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WO2008050715A1 - Metal-film-coated material and process for producing the same, metallic-pattern-bearing material and process for producing the same, composition for polymer layer formation, nitrile polymer and method of synthesizing the same, composition containing nitrile polymer, and layered product - Google Patents

Metal-film-coated material and process for producing the same, metallic-pattern-bearing material and process for producing the same, composition for polymer layer formation, nitrile polymer and method of synthesizing the same, composition containing nitrile polymer, and layered product Download PDF

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Publication number
WO2008050715A1
WO2008050715A1 PCT/JP2007/070545 JP2007070545W WO2008050715A1 WO 2008050715 A1 WO2008050715 A1 WO 2008050715A1 JP 2007070545 W JP2007070545 W JP 2007070545W WO 2008050715 A1 WO2008050715 A1 WO 2008050715A1
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WO
WIPO (PCT)
Prior art keywords
group
polymer
formula
substrate
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/070545
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French (fr)
Japanese (ja)
Inventor
Takeyoshi Kano
Hideo Nagasaki
Masataka Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2007256746A external-priority patent/JP5164502B2/en
Priority claimed from JP2007256745A external-priority patent/JP5106025B2/en
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to KR1020097001569A priority Critical patent/KR101459515B1/en
Priority to EP07830279.1A priority patent/EP2078607B1/en
Priority to CN2007800394054A priority patent/CN101528458B/en
Priority to US12/446,722 priority patent/US20100003533A1/en
Publication of WO2008050715A1 publication Critical patent/WO2008050715A1/en
Anticipated expiration legal-status Critical
Priority to US12/433,034 priority patent/US8084564B2/en
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/30—Nitriles
    • C08F22/32—Alpha-cyano-acrylic acid; Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/50—Nitriles containing four or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/121—Metallo-organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a method for producing a surface metal film material, a surface metal film material, a method for producing a metal pattern material, a metal pattern material, and a polymer layer forming composition.
  • the present invention also relates to a novel polymer containing a nitrile group and a polymerizable group, a synthesis method thereof, a composition containing the polymer, and a laminate comprising the composition.
  • the “subtractive method” is mainly used as a method for producing force and metal pattern materials.
  • a photosensitive layer that is exposed to actinic rays is provided on a metal film formed on the surface of the substrate, this photosensitive layer is exposed imagewise, and then developed to form a resist image.
  • the metal film is etched to form a metal pattern, and finally the resist is peeled off.
  • a graft polymer having a polar group remains at the interface portion of the board, so that moisture ions and the like are easily retained. Therefore, there were concerns about temperature and humidity dependence, resistance to ion migration between wires, and changes in shape. In particular, when applied to fine wiring such as printed wiring boards, high insulation between wirings (metal patterns) is required, and further improvement in insulation reliability between wirings is required. Currently.
  • the photocurable resin composition is not only used as a material for surface treatment as described above, but also as a resist material, a printing plate material, a coating material, an optical modeling material, and the like. Used.
  • the material that is cured by radical polymerization is generally composed of a binder, a polyfunctional monomer, and a photopolymerization initiator. In this case, as a method for improving the photocuring sensitivity, there is a method using a binder having a polymerizable group.
  • a surface treatment material particularly a surface treatment material for forming a plating film, needs a function of adsorbing a plating catalyst.
  • carboxylic acid groups, hydroxyl groups, ether groups, and the like are known as adsorptive groups for the plating catalyst, but these functional groups are highly hydrophilic and easily retain moisture, ions, etc.
  • the formed film would depend on the temperature / humidity of the attached film and would affect the shape change.
  • Patent Document 2 describes the following macromonomer c
  • the macromonomer described above has a low curability (polymerizability) with a small amount of polymerizable groups in the polymer, and also has a low content of cyan groups in the polymer molecule. was there.
  • Patent Document 1 JP-A-11 106372
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-176025
  • Non-Patent Document 1 Advanced Materials 2000 No. 20 1481— 1494
  • the present invention has been made in consideration of the above-mentioned drawbacks of the conventional techniques.
  • the present invention provides a surface metal film material that is excellent in adhesion of a metal film and has little fluctuation in adhesion due to changes in humidity, and a method for producing the same.
  • the present invention provides a metal pattern material excellent in insulation reliability in a region where a metal pattern is not formed, and a method for manufacturing the same.
  • the present invention provides a composition for forming a polymer layer that can form a polymer layer that has low water absorption and high hydrophobicity, and that is excellent in adsorption to the plating catalyst or its precursor.
  • the present invention provides a novel polymer having sufficient adsorptivity to a metal such as a plating catalyst and excellent in polymerizability, a composition using the same, and a laminate.
  • the present invention provides a method for producing a first surface metal film material comprising: (al) a functional group that forms an interaction with a plating catalyst or a precursor thereof on a substrate; Chemical bond A step of forming a polymer layer comprising the polymer obtained, (a2) a step of applying a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of performing a test on the plating catalyst or the precursor thereof. And the polymer layer satisfies all of the following conditions 1 to 4.
  • Condition 1 25 ° C—Saturated water absorption in a 50% relative humidity environment is 0.01 to 10 mass%
  • Condition 2 25 ° C—Saturated water absorption in a 95% relative humidity environment is 0.05 to 20 mass %
  • Condition 3 Water absorption after immersion in boiling water at 100 ° C for 1 hour is 0;
  • Condition 4 25 ° C — In a 50% relative humidity environment, 5 ⁇ L of distilled water is dropped and the surface contact angle after standing for 15 seconds is 50 to 150 degrees.
  • the polymer layer is: It is preferable to satisfy all the conditions of ' ⁇ 4'.
  • Condition 1 25 ° C—Saturated water absorption at 50% relative humidity is 0.0; 0 to 5% by mass Condition 2': 25 ° C—Saturated water absorption at 95% relative humidity is 0.05 ⁇ ; 10% by mass Condition 3 ': Saturated water absorption after immersion in boiling water at 100 ° C for 1 hour is 0.;! ⁇ 20% by mass Condition 4': 25 ° C-distilled at 50% relative humidity The surface contact angle after dropping for 5 seconds and standing for 15 seconds is 55 to 150 degrees.
  • step (al) in the present invention is performed by directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor on the substrate. Is preferred!
  • the (al) step includes (al-1) a step of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; al-2) It is also preferable that the polymerization initiating layer includes a chemical group directly having a functional group that interacts with the plating catalyst or its precursor and a polymer having a polymerizable group. is there.
  • a polymer having a functional group that interacts with the plating catalyst or a precursor thereof, and a polymerizable group includes a unit represented by the following formula (1), and the following formula (2 It is preferable that it is a copolymer containing the unit represented by this.
  • the weight average molecular weight of the polymer having a functional group that forms an interaction with the metal catalyst or its precursor and a polymerizable group is 20000 or more.
  • the second surface metal film material production method of the present invention includes a step of forming a polymer layer made of a polymer having a cyano group and directly bonded to the substrate on an (al ') substrate. And (a2) a step of imparting a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of performing contact with the plating catalyst or the precursor thereof.
  • the (al ′) step is preferably performed by directly chemically bonding a polymer having a cyano group and a polymerizable group on a substrate.
  • the (al ′) step is a step of producing a substrate in which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a (al-1 ′) base material; It is also a preferred embodiment that (al-2 ′) contains a polymer having a cyano group and a polymerizable group directly chemically bonded to the polymerization initiation layer.
  • the weight average molecular weight of the polymer having a cyano group and a polymerizable group is preferably 20000 or more.
  • step (a3) it is preferable that electroless plating is performed. It is more preferable that electrical plating is further performed after the electroless plating.
  • the plating catalyst used in the step (a2) in the present invention is preferably palladium.
  • the third surface metal film material production method of the present invention comprises (al ") a functional group that interacts with the plating catalyst or its precursor on both sides of the resin film, and A step of forming a polymer layer comprising a polymer directly chemically bonded to the substrate; (a2) a step of applying a plating catalyst or a precursor thereof to the polymer layer; and (a3) the plating catalyst or a precursor thereof. And a step of performing tapping, wherein the polymer layer satisfies all of the following conditions;
  • Condition 1 25 ° C—Saturated water absorption in a 50% relative humidity environment is 0.01 to 10 mass%
  • Condition 2 25 ° C—Saturated water absorption in a 95% relative humidity environment is 0.05 to 20 mass %
  • Condition 3 The water absorption after immersion in boiling water at 100 ° C for 1 hour is 0.;! ⁇ 30% by mass
  • Condition 4 25 ° C—50% relative humidity is added dropwise with 5 ⁇ L of distilled water. Surface contact angle after standing for 15 seconds is 50 to 150 degrees
  • a resin film is used as a substrate and a polymer layer is formed on both sides by the (al ") step.
  • a surface metal film material having a metal film formed on both surfaces can be obtained.
  • the step (al "), the step (a2), and the step (a3) are preferably performed simultaneously on both sides of the resin film for each step.
  • the surface metal film material of the present invention is obtained by the method for producing a surface metal film material of the present invention.
  • the first polymer layer forming composition of the present invention contains a polymer having a cyano group and a polymerizable group, and a solvent capable of dissolving the polymer, and the surface metal film material of the present invention. It is used for the production method of
  • the second polymer layer-forming composition of the present invention comprises O (CH) O (n is;
  • a polymer having a polymerizable group and a solvent capable of dissolving the polymer is used in the method for producing a surface metal film material of the present invention.
  • the method for producing a metal pattern material of the present invention comprises (a4) a step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material of the present invention into a pattern.
  • the metal pattern material is produced by performing the steps (al), (a2), and (a3) in the above-described surface metal film material production method, and then etching the masked film into a pattern. Step [Step (a4)] is performed.
  • the metal pattern material of the present invention is obtained by the method for producing a metal pattern material of the present invention.
  • the present invention also provides a polymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2).
  • ⁇ ⁇ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y and Z each independently represent a single bond, a substituted or unsubstituted divalent organic group, an ester group, Represents an amide group or an ether group, and L 1 and L 2 are each independently Represents a substituted or unsubstituted divalent organic group.
  • the unit represented by the formula (1) is preferably a unit represented by the following formula (3).
  • R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond, a substituted or unsubstituted divalent organic group.
  • Group represents an ester group, an amide group, or an ether group
  • W represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group)
  • L 1 represents a substituted or unsubstituted divalent group.
  • the unit represented by the formula (3) is a unit represented by the following formula (4).
  • R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group
  • V and W each independently represent an oxygen atom or NR ( R represents a hydrogen atom or an alkyl group.)
  • L 1 represents a substituted or unsubstituted divalent organic group.
  • W is preferably an oxygen atom.
  • L 1 in the formula (1), formula (3), or formula (4) is a divalent organic group having a urethane bond or a urea bond.
  • L 1 in the formula (1), formula (3), or formula (4) is a divalent organic group having 1 to 9 total carbon atoms.
  • the unit represented by the formula (2) is preferably a unit represented by the following formula (5).
  • R 5 represents a hydrogen atom or a substituted or unsubstituted alkyl group
  • U represents an oxygen atom
  • NR ′ R ′ represents a hydrogen atom or an alkyl group
  • L 2 represents a substituted or unsubstituted divalent organic group.
  • Connection site strength with the cyan group in L 2 in the above formula (5) is preferably a divalent organic group having a linear, branched, or cyclic alkylene group. More preferably, the divalent organic group having a linear, branched, or cyclic alkylene group at the linking site has a total carbon number;
  • the divalent organic group is a divalent organic group having an aromatic group, which has an aromatic group at the site connected to the cyano group in L 5 in the formula (5). More preferably, the divalent organic group has a total carbon number of 6 to 15;
  • L 1 in the formula (1), formula (3), or formula (4) is preferably a divalent organic group having a urethane bond.
  • the novel polymer preferably has a weight average molecular weight of 20,000 or more.
  • the polymer synthesis method of the present invention uses a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group at least in a solvent.
  • a urethane bond in L 1 is formed by adding the isocyanate group to a xyl group.
  • a hydroxyl group-containing (meth) acrylate obtained by sequentially polymerizing a polymer having a hydroxyl group in the side chain through the following steps (1) to (4): It is preferred that it is synthesized using.
  • the solvent used is preferably an ester solvent having an SP value (calculated by the Okitsu method) of 20 to 23 MPa 1/2. More preferred is a diacetate solvent.
  • the composition of the present invention is characterized by containing the polymer of the present invention and a ketone solvent or a nitrile solvent, and in particular, the concentration force of the polymer in the composition is 2 mass% to 50 mass%. mass
  • the laminate of the present invention is characterized in that the composition of the present invention is applied on a resin substrate.
  • the present invention it is possible to provide a surface metal film material that is excellent in adhesion of a metal film and has little fluctuation in adhesion due to humidity change, and a method for manufacturing the same.
  • the metal pattern having excellent insulation reliability in the non-formation region of the metal pattern.
  • a turn material and a manufacturing method thereof can be provided.
  • composition for forming a polymer layer that can form a polymer layer that has a low water absorption and a high hydrophobicity, and further has an excellent adsorptivity to the plating catalyst or its precursor. Monkey.
  • a novel polymer having sufficient adsorptivity to a metal such as a plating catalyst, and also excellent in polymerizability, a synthesis method thereof, a composition using the novel polymer, and lamination The body can be provided.
  • the substrate has a functional group that interacts with a plating catalyst or a precursor thereof, and is directly chemically bonded to the substrate.
  • Condition 1 25 ° C.—Saturated water absorption in a 50% relative humidity environment is 0.01 to 10; Mass% Condition 2: Saturated water absorption rate at 25 ° C-95% relative humidity is 0.05 to 20% by mass Condition 3: Water absorption rate after immersion in boiling water at 100 ° C for 1 hour is 0.; 30% by mass Condition 4: 25 ° C-50% relative humidity In a 5% L distilled water drop, the surface contact angle after standing for 15 seconds is 50 to 150 degrees
  • a polymer layer made of a polymer having a cyano group and directly chemically bonded to the substrate is formed on the (al ') substrate. And (a2) a step of imparting a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of attaching the plating catalyst or the precursor thereof. And
  • the method for producing a metal pattern material of the present invention comprises (a4) a step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material of the present invention into a pattern.
  • the metal pattern material is produced by performing the steps (al), (al ′), (a2), and (a3) in the method for producing the surface metal film material.
  • the step of etching into a pattern [step (a4)] is performed.
  • the polymer layer satisfying the above four conditions has low water absorption even under high temperature and high humidity. , Have high hydrophobicity.
  • the polymer layer formed by the method for producing the second surface metal film material of the present invention has low water absorption and high hydrophobicity even under high temperature and high humidity.
  • a metal film having excellent adhesion to the polymer layer can be obtained by applying a plating catalyst or the like to the polymer layer composed of the polymer bonded to the substrate and then performing plating using the catalyst.
  • the obtained surface metal film material has a metal film with excellent adhesion to the substrate, and the polymer layer does not change according to the humidity change. Will be less.
  • Such a surface metal film material is applied to a method for producing a metal pattern material, which will be described later, and can be used as an electromagnetic wave prevention film, a shield material, etc., in addition to being used as an electric wiring material.
  • step (a4) the metal pattern is not formed by obtaining a metal pattern by etching the cover film formed on the entire surface of the substrate in a pattern. Even if the polymer layer is exposed in the region, the exposed portion does not absorb water and the insulation is not lowered. As a result, the metal pattern material formed in the method for producing the metal pattern material of the present invention has excellent insulation reliability in the non-formation region of the metal pattern.
  • the saturated water absorption rate and water absorption rate under conditions 1 to 3 can be measured by the following method. First, the substrate is left in a vacuum dryer to remove moisture contained in the substrate, and then the conditions 1 and 2 If this is the case, leave it in a constant temperature and humidity chamber set to the desired temperature and humidity. In this case, immerse in a water bath with boiling water at 100 ° C for 1 hour, and measure the saturated water absorption and water absorption by measuring mass change.
  • the saturated water absorption rate under conditions 1 and 2 indicates the water absorption rate when the mass does not change after 24 hours.
  • the water absorption rate of the substrate and the laminate are measured by measuring the saturated water absorption rate and the water absorption rate of the laminate in the same manner.
  • the water absorption rate of the polymer layer can be measured by the difference from the water absorption rate.
  • a petri dish or the like without providing a polymer layer on the substrate, a single polymer film constituting the polymer layer was prepared, and the resulting single polymer film was directly measured for water absorption by the above method. May be.
  • the contact angle in Condition 4 can be measured by the following method.
  • a laminate in which a polymer layer is formed on a substrate is prepared, and stored in a constant temperature and humidity chamber set at 25 ° C_50% relative humidity.
  • a surface contact angle contact angle measurement device (trade name: OCA20, manufactured by Data physics) in a measurement chamber adjusted to 25 ° C—50% relative humidity
  • the stored sample is a substrate (polymer layer) 5 L of distilled water is automatically dropped from the syringe on the top, the image in the cross-sectional direction of the substrate is taken into a personal computer by a CCD camera, and the contact angle of the water droplet on the substrate (polymer layer) is numerically calculated by image analysis.
  • the polymer layer obtained in the step (al) is: It is preferable to satisfy all the conditions of “ ⁇ 4”.
  • Condition 1 25 ° C—Saturated water absorption at 50% relative humidity is 0.0; 0 to 5% by mass Condition 2': 25 ° C—Saturated water absorption at 95% relative humidity is 0.05 ⁇ ; 10% by mass Condition 3 ': Water absorption after immersion in boiling water at 100 ° C for 1 hour is 0.;! ⁇ 20% by mass Condition 4': 25 ° C—distilled water at 50% relative humidity 5
  • the surface contact angle after standing for 15 seconds is 55 to 150 degrees.
  • the polymer constituting the polymer layer may be a polymer having low water absorption or hydrophobicity.
  • a method using a material having a low hydrophilicity (low hydrophilicity) a method of adding a substance that lowers water absorption or a substance that improves hydrophobicity to the polymer layer, and after forming the polymer layer Soak in a solution containing a reactive substance that hydrophobizes the polymer molecules forming the polymer layer. Examples of methods include soaking and hydrophobizing polymers and their reactive substances.
  • a functional group (hereinafter simply referred to as “interactive group”) that forms an interaction with the plating catalyst or its precursor on the substrate.
  • a polymer layer made of a polymer that is directly chemically bonded to the substrate.
  • This polymer layer is required to satisfy all the above conditions 1 to 4.
  • the step (al) is preferably performed by directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor on the substrate.
  • the (al) step includes (al-1) a step of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; al-2) It is also a preferred embodiment that the polymerization initiating layer is a step of forming a polymer layer comprising a polymer having an interactive group and directly chemically bonded to the polymerization initiating layer.
  • step (al-2) after the polymer having a polymerizable group and an interactive group is brought into contact with the polymerization initiation layer, energy is applied to the entire substrate surface (polymerization initiation).
  • the process is preferably a process in which the polymer is directly chemically bonded to the entire surface of the layer.
  • Graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on the polymer compound chain and further polymerizing another monomer that initiates polymerization. is there.
  • this is called surface draft polymerization.
  • any known method described in the literature can be used.
  • New Polymer Experiment 10, edited by Polymer Society of Japan, 1994, published by Kyoritsu Shuppan Co., Ltd., pl35 describes photograft polymerization and plasma irradiation graft polymerization as surface graft polymerization methods.
  • photograft polymerization method examples include the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413.
  • a trialkoxysilyl group, isocyanate group, amino group is added to the end of the polymer compound chain. It is possible to apply a method in which a reactive functional group such as a group, a hydroxyl group, or a carboxyl group is added and bonded by a coupling reaction between the functional group and the functional group present on the substrate surface.
  • a polymer layer using a photograft polymerization method, particularly a photograft polymerization method using UV light.
  • the “substrate” in the method for producing a surface metal film material of the present invention is a function that can form a state in which a polymer having a functional group that interacts with a plating catalyst or a precursor thereof is directly chemically bonded.
  • the substrate itself may have such surface characteristics to constitute the substrate, and a separate intermediate layer (for example, a polymerization initiation layer described later) is provided on the substrate.
  • the intermediate layer may have such characteristics to constitute the substrate.
  • An example of the substrate used in the present invention is preferably a dimensionally stable plate.
  • Paper, plastic eg, polyethylene, polypropylene, polystyrene, etc. laminated, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, propion) Acid cellulose, butanolic acid senololose, acetylenic acetate, senorelose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polybulacetal, polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.)
  • paper or plastic film on which a metal as described above is laminated or vapor-deposited are included.
  • an epoxy resin or a polyimide resin is preferable.
  • the substrate It may be used as a substrate.
  • a base material containing polyimide having a polymerization initiation site in the skeleton described in paragraphs [0028] to [0088] of JP-A-2005-281350 can also be used.
  • the metal pattern material obtained by the method for producing a metal pattern material of the present invention can be applied to a semiconductor package, various electric wiring boards, and the like.
  • a substrate containing an insulating resin as shown below.
  • a substrate made of an insulating resin or a substrate having a layer made of an insulating resin on a base material it is preferable to use a substrate made of an insulating resin or a substrate having a layer made of an insulating resin on a base material.
  • a known insulating resin composition is used.
  • various additives can be used in combination with the insulating resin composition depending on the purpose. For example, for the purpose of increasing the strength of the insulating layer, a polyfunctional acrylate monomer is added, or for the purpose of increasing the strength of the insulating layer and improving the electrical characteristics, inorganic or organic particles are added, etc. Measures can also be taken.
  • the “insulating resin” in the present invention means a resin having a degree of insulation that can be used for a known insulating film or insulating layer. thing However, any resin having an insulating property according to the purpose can be applied to the present invention.
  • the insulating resin may be a thermosetting resin, a thermoplastic resin, or a mixture thereof! /.
  • the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, and the like.
  • epoxy resin examples include cresol nopolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol nopolak type epoxy resin, alkylphenol nopolac type epoxy resin, biphenol F type epoxy resin. , Naphthalene type epoxy resins, dicyclopentagen type epoxy resins, epoxidized products of condensates of phenols with aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resins and the like. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.
  • polystyrene resin examples include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, a cycloolefin resin, and copolymers of these resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ethereol, polyether imide, and the like.
  • thermoplastic resins include 1,2-bis (buhlylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or modified resins of this with polyphenylene ether resins (Satoru Ama et al., Journal of Applied Polymer Science VoL92, 1252-1258 (2004)), liquid crystalline polymers (specifically, Kuraray Betastar, etc.), fluororesin (PTFE), and the like.
  • thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is done for the purpose of compensating each defect and producing a better effect.
  • thermoplastic resins such as polyphenylene ether (PPE) have low resistance to heat, and are therefore alloyed with thermosetting resins.
  • PPE polyphenylene ether
  • Cyanate ester is a resin that has excellent dielectric properties in thermosetting properties, but is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin.
  • thermosetting resin containing an epoxy resin and / or a phenol resin and a thermoplastic resin containing a phenoxy resin and / or polyether sulfone (PES) are also used for improving the dielectric properties.
  • the insulating resin composition may contain a compound having a polymerizable double bond in order to promote crosslinking, specifically, an acrylate or metatalylate compound. Sensory ones are preferred.
  • a compound having a polymerizable double bond a thermosetting resin or a thermoplastic resin such as an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, methacrylic acid, acrylic acid, or the like is used.
  • a resin in which a part of the resin is (meth) acrylated.
  • the insulating resin composition according to the present invention includes a resin and other components in order to enhance the properties of the resin film such as mechanical strength, heat resistance, weather resistance, flame retardancy, water resistance, and electrical properties.
  • a resin and other components in order to enhance the properties of the resin film such as mechanical strength, heat resistance, weather resistance, flame retardancy, water resistance, and electrical properties.
  • Other composites can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluororesin, and polyphenylene oxide resin.
  • the insulating resin composition can be used for a general resin material for a wiring board, if necessary, for example, silica, alumina, clay, talc, aluminum hydroxide, carbonic acid, ruthenium, etc.
  • Inorganic fillers, cured epoxy resins, cross-linked benzoguanamine resins, cross-linked acrylic polymers and other organic fillers may be used alone or in combination.
  • silica is the preferred filler.
  • the insulating resin composition may contain various additives such as a colorant, a flame retardant, an adhesive agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. You can add two or more.
  • these materials are added to the insulating resin composition, it is preferable to add them in the range of 1 to 200% by mass with respect to the resin, more preferably 10 to 80% by mass. Range of Added in a box. If the amount added is less than 1% by mass, the effect of enhancing the above properties is not obtained. If the amount added exceeds 200% by mass, properties such as strength peculiar to the resin are deteriorated.
  • the dielectric constant and dielectric loss tangent of the insulating resin can be measured by a conventional method.
  • the cavity resonator perturbation method for example, ⁇ r, tan ⁇ measuring device for ultra-thin sheet, key, based on the method described in “18th Annual Meeting of the Japan Institute of Electronics Packaging”, pi 89, 2004. It can be measured using Ichicom Co., Ltd.).
  • Insulating resins having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.01 or less include liquid crystal polymers, polyimide resins, fluororesins, polyphenylene ether resins, cyanate ester resins, bis (bisphenylenes). ) Ethane resins and the like, and further modified resins thereof.
  • the substrate used in the present invention has surface irregularities of preferably 500 nm or less, more preferably lOOnm or less, and even more preferably 50 nm or less, in consideration of applications to semiconductor packages, various electric wiring boards, and the like. Most preferably, it is 20 nm or less.
  • surface irregularity of this substrate surface irregularity of the layer when an intermediate layer or polymerization initiation layer is provided
  • it is preferable because electric loss is reduced.
  • the substrate is a plate-like material, for example, a resin film (plastic film)
  • the polymer layer is formed on both surfaces of the resin film by performing an (al) process on both surfaces. (In the method for producing the third surface metal film material of the present invention, (al ”)).
  • a polymerization initiator is contained on the base material when the graft polymer is generated.
  • a substrate on which a polymerization initiating layer having a functional group capable of initiating polymerization is formed By using this substrate, active sites can be generated efficiently and more graft polymers can be generated.
  • a polymerization initiating layer in the present invention will be described. If the substrate is a plate-like material, a polymerization initiating layer may be formed on both sides thereof.
  • Examples of the polymerization initiating layer in the present invention include a layer containing a polymer compound and a polymerization initiator, a layer containing a polymerizable compound and a polymerization initiator, and a layer having a functional group capable of initiating polymerization.
  • the polymerization initiating layer in the present invention can be formed by dissolving the necessary components in a solvent that can be dissolved, providing the components on the surface of the substrate by a method such as coating, and hardening by heating or light irradiation.
  • the compound used in the polymerization initiation layer in the present invention is not particularly limited as long as it has good adhesion to the substrate and generates active species by applying energy such as irradiation with actinic rays. Can be used. Specifically, a mixture of a polyfunctional monomer or a hydrophobic polymer having a polymerizable group in the molecule and a polymerization initiator can be used.
  • hydrophobic polymer having a polymerizable group in the molecule examples include gen-based homopolymers such as polybutaene, polyisoprene, and polypentagen, —Homopolymers of aryl-containing monomers such as aryloxetyl methacrylate
  • Binary or multi-component copolymers such as styrene, (meth) acrylic acid ester, (meth) atrylonitrile, etc., containing gen-based monomers such as butadiene, isoprene and pentagene or aryl group-containing monomers as constituent units; Linear polymer having carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, high density polyethylene, etc.
  • Three-dimensional polymers are three-dimensional polymers; and the like.
  • the content of these polymerizable compounds is particularly preferably in the range of 10 to 80% by mass, preferably in the range of 10 to;
  • the polymerization initiation layer contains a polymerization initiator for expressing the polymerization initiation ability by applying energy.
  • the polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit a polymerization initiating ability by predetermined energy, for example, irradiation with active light beam, heating, electron beam irradiation, and the like. Depending on the purpose, it can be appropriately selected and used. Among these, it is preferable to use photopolymerization from the viewpoint of production suitability, and therefore it is preferable to use a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it is active with respect to the irradiated actinic ray and can be surface-grafted from the polymerization initiation layer containing the photopolymerization initiator, for example, a radiocanole polymerization initiator or an anion polymerization starter.
  • An agent, a cationic polymerization initiator, and the like can be used. From the viewpoint of ease of handling and reactivity, a radical polymerization initiator and a cationic polymerization initiator are preferred, and a radical polymerization initiator is preferred.
  • photopolymerization initiator examples include, for example, p tert butyl trichloroacetophenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methinoleyl 1-phenylpropane.
  • Acetofenones such as 1-one; Ketones such as benzophenone (4, 4, 1 bisdimethinoreaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthiorexanthone, 2-isopropylthioxanthone; Benzoin etherenoles such as benzoin, benzoin methinoreethenole, benzoin isopropinoleethenore, benzoin isop, chinolee tenole; penzinoresimethinoreketanol, and hydroxycyclohexyl phenyl ketone Nilketals; triphenylsulfonium chloride , A Yodoniumu salts such as door Lihue Nino less Norre Honi ⁇ -time Sunorehoniumu salt such as a pen tough Norre Oro phosphate, Jifue two Norre ® over Denis ⁇ skeleton
  • the content of the polymerization initiator is preferably in the range of 0.;! To 70% by mass in solid content in the polymerization initiator layer; particularly preferably in the range of!
  • the solvent used in applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferred. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
  • acetone methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, tonoleene, ethylene glycol monomethino ethenore, ethylene glycol monomethino ethenore, ethylene glyconoresin methino rea.
  • Tenole Propylene glycol monomethyl ether, Propylene glycol monoethyl ether, Acetyl acetone, Cyclohexanone, Methanol, Ethanol, 1-Methoxy-2-propanol, 3-Methoxyprononore, Diethylene glycol !; Noreetenore, Diethylenegu!
  • the concentration of the solid content in the coating solution is suitably 2 to 50% by mass.
  • the coating amount when the polymerization initiating layer is formed on the substrate is such that the sufficient polymerization initiating ability is exhibited, and from the viewpoint of preventing film peeling by maintaining film properties, By weight, 0.;! To 20 g / m 2 force S preferred, 0.;! To 15 g / m 2 more preferred 0.;! To 2 g / m 2 more preferred.
  • the composition for forming a polymerization initiation layer is disposed on a base material by coating or the like, and a film is formed by removing the solvent to form a polymerization initiation layer. 1S
  • the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is preliminarily cured to some extent, so that the polymerization starts after the graft polymer is formed on the polymerization initiation layer. If you drop off the layer, it is preferable because you can effectively suppress the situation!
  • the heating temperature and time may be selected so that the coating solvent can be sufficiently dried, but from the point of production suitability, the temperature is 100 ° C or less and the drying time is preferably within 30 minutes. It is more preferable to select heating conditions in the range of 80 ° C and drying time within 10 minutes.
  • Light irradiation performed as desired after heat-drying can be performed using a light source used for a graft polymer formation reaction described later.
  • the active point of the polymerization initiating layer generated by the application of energy and the fact that it does not inhibit the formation of the graft polymer are present in the polymerization initiating layer.
  • the light irradiation time varies depending on the intensity of the light source. In general, it is preferably within 30 minutes.
  • the film remaining rate after solvent cleaning is 80% or less and the initiator remaining rate after pre-curing is 1% or more.
  • polymerization initiation using a polymer in which a polymerization initiating group described in JP-A-20004-161995 is pendant on a side chain is used.
  • a layer is also preferred.
  • this polymer is a polymer having a functional group (polymerization initiating group) having a polymerization initiating ability in the side chain and a crosslinkable group (hereinafter referred to as a polymerization initiating polymer). It is possible to form a polymerization initiating layer having a polymerization initiating group bonded to a chain and having the polymer chain immobilized by a crosslinking reaction.
  • the polymerization initiating layer thus formed is also suitable as the polymerization initiating layer of the present application.
  • polymerization initiating polymers include the following.
  • the polymerization initiating layer using the polymerization initiating polymer in the present invention is prepared by dissolving the above-mentioned polymerization initiating polymer in an appropriate solvent, preparing a coating solution, and arranging the coating solution on a substrate by coating or the like.
  • the film is formed by removing the solvent and proceeding with the crosslinking reaction.
  • the polymerization initiating polymer is immobilized as the bridge reaction proceeds.
  • the immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a polymerization initiating polymer and a method using a crosslinking agent together, and it is preferable to use a crosslinking agent.
  • Self-condensation reaction of polymerization initiator polymer As an example of the method using the reaction, when the crosslinkable group is NCO, there is a method using the property that the self-condensation reaction proceeds by applying heat. As this self-condensation reaction proceeds, a crosslinked structure can be formed.
  • crosslinking agent used in the method in which the crosslinking agent is used in combination conventionally known crosslinking agents such as those described in Shinji Yamashita's “Crosslinking agent handbook” can be used.
  • crosslinkable group, crosslinker (COOH, polyvalent amine), (-COOH, polyvalent aziridine), (-COO H, multiple -Valent isocyanate), (-COOH, polyvalent epoxy), (-NH2, polyvalent isocyanate)
  • crosslinking agent in the present invention include those having the following structures.
  • Such a crosslinking agent is added to the coating solution containing the above-mentioned polymerization initiating polymer when the polymerization initiating layer is formed. After that, the crosslinking reaction proceeds by the heat at the time of drying the coating film, A strong cross-linked structure can be formed. More specifically, a crosslinking reaction proceeds by a dehydration reaction shown by exl. Below or an addition reaction shown by ex2. A crosslinked structure is formed. The temperature condition in these reactions is preferably 50 ° C or higher and 300 ° C or lower, more preferably 80 ° C or higher and 200 ° C or lower.
  • the addition amount of the crosslinking agent in the coating solution varies depending on the amount of the crosslinkable group introduced into the polymerization initiating polymer. However, the degree of crosslinking and the polymerization reaction due to residual unreacted crosslinking components remain. From the viewpoint of the influence on the number of moles, it is usually preferable that the amount is 0.0;! To 50 equivalents relative to the number of moles of the crosslinkable group, and that 0.01 to 10 equivalents is more preferable. More preferably, it is ⁇ 3 equivalents.
  • the solvent used for applying the polymerization initiating layer is not particularly limited as long as the above-mentioned polymerization initiating polymer can be dissolved. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferred. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
  • acetone methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, tonoleene, ethylene glycol monomethino ethenore, ethylene glycol monomethino ethenore, ethylene glyconoresin methino rea.
  • Cornole monoethylenoate diethylene glyconoresin methinore etherenore, diethylene glycono lesino ethenore, propylene glycoleno monomethino ethenore acetate, propylene glycol monoleethyl ether acetate, 3-methoxypropyl acetate and the like. These solvents can be used alone or in combination.
  • the concentration of the solid content in the coating solution is suitably 2 to 50% by mass.
  • the coating amount of the polymerization initiating layer using the polymerization initiating polymer is preferably from 0.;! To 20 g / m 2 in terms of the mass after drying from the viewpoint of the ability to initiate surface graft polymerization and film properties. More preferably, !-15 g / m 2 is preferred.
  • a known polymerization initiator is contained in the layer made of the insulating resin.
  • an insulating polymerization initiating layer is preferable.
  • the polymerization initiator contained in the insulating polymerization initiator layer is not particularly limited.For example, the above-described thermal polymerization initiator, photopolymerization initiator (radical polymerization initiator, cation polymerization initiator, cationic polymerization initiator).
  • a polymer compound having an active carbonyl group described in JP-A-9 77891 and JP-A-10-45927 in the side chain and further, a functional group having a polymerization initiating ability in the side chain and a crosslinking property
  • a polymer having a group (polymerization initiating polymer) or the like can be used.
  • the amount of the polymerization initiator contained in the insulating polymerization initiating layer is preferably about 0.;! To 50% by mass in terms of solid content in the insulating layer. 1. 0-30 More preferably, it is about 0% by mass.
  • the graft polymer is generated by using a coupling reaction between the functional group present on the substrate surface as described above and the reactive functional group of the polymer compound at its terminal or side chain.
  • a photograft polymerization method can be used.
  • a substrate having a polymerization initiating layer formed on a substrate is used, and the polymerization initiating layer has a functional group (interactive group) that forms an interaction with the plating catalyst or its precursor.
  • a polymer layer composed of a polymer directly chemically bonded to the polymerization initiation layer [(al-2) step] is preferable. More preferably, a polymerizable group is formed on the polymerization initiating layer.
  • energy is applied to the polymer to directly chemically bond the polymer to the entire substrate surface (the entire polymerization initiation layer surface). That is, a composition containing a compound having a polymerizable group and an interactive group is directly bonded to the surface of the polymerization initiation layer while being brought into contact with the active species generated on the surface of the polymerization initiation layer.
  • the substrate on which the polymerization initiating layer is formed is immersed in a liquid composition containing the compound having a polymerizable group and an interactive group (the composition for forming a polymer layer of the present invention).
  • a composition containing a compound having a polymerizable group and an interactive group (the composition for forming a polymer layer of the present invention). It is preferable to form a layer composed of a product on the substrate surface (polymerization initiation layer surface) by a coating method.
  • the compound having a polymerizable group and an interactive group in the present invention includes a polymerizable group and an interactive group so that the polymer layer formed of the generated graph polymer satisfies all the conditions of! In addition, it is preferable to use a compound having low water absorption and high hydrophobicity.
  • the interactive group in this compound is preferably a non-dissociable functional group.
  • the non-dissociable functional group means a functional group that does not generate a proton upon dissociation.
  • Such a functional group has a function of forming an interaction with the plating catalyst or its precursor, but does not have high water absorption and hydrophilicity unlike a dissociative polar group (hydrophilic group).
  • the polymer layer composed of the graft polymer having this functional group can satisfy the above-mentioned conditions!
  • the polymerizable group in the present invention is a compound between a compound having a polymerizable group and an interactive group, or a compound having a polymerizable group and an interactive group and a substrate by energy application. Specifically, it is a functional group that binds, specifically in a bur group, a buroxy group, an allyl group, an attalyl group, a methacryloyl group, an oxetane group, an epoxy group, an isocyanate group, a functional group containing an active hydrogen, or an azo compound. An active group etc. are mentioned.
  • a group capable of forming a coordination with a metal ion, a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group and the like are preferable.
  • Nitrogen-containing functional groups such as azide group, cyano group, cyanate group (R—OCN), ether group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, N-hydroxy structure
  • Oxygen-containing functional groups such as thioether groups, thioether groups, thioxyl groups, sulfoxide groups, sulfone groups, sulfite groups, groups containing sulfoxymine structures, groups containing sulfoxum salt structures, sulfonic acid esters
  • Sulfur-containing officers functional group such as a group containing a structure, phosphorus-containing functional groups, such as phosphine group, chlorine, a group containing a halogen atom such as bromine, and unsaturated ethylenic group and the like.
  • an imidazole group, a urea group, or a thiourea group may be used as long as it is non-dissociative due
  • the ether group specifically has a structure represented by O (CH) O (where n is an integer of 1 to 5), or cyan Base
  • a particularly preferred cyano group is mentioned as the most preferred one.
  • the force that tends to increase the water absorption as the polarity becomes higher.
  • the cyan groups interact in the polymer layer so as to cancel each other's polarity, so that the film becomes dense and Since the polarity of the entire polymer layer is lowered, the water absorption is lowered.
  • the cyano group is solvated and the interaction between the cyano groups is eliminated, and the interaction with the plating catalyst can be achieved.
  • a polymer layer having a cyano group is preferred in that it exhibits low performance while exhibiting contradictory performance that interacts well with the plating catalyst.
  • the interactive group in the present invention is more preferably an alkyl cyano group. This is because the aromatic cyano group attracts electrons to the aromatic ring, leading to a plating catalyst, etc. Although the donating property of unpaired electrons, which is important as the adsorptive property of the metal, is low, the alkyl cyano group is preferred because of its adsorptive properties to the plating catalyst, etc. ,.
  • the compound having a polymerizable group and an interactive group may be in any form of a monomer, a macromonomer, and a polymer, and the formability of the polymer layer and the ease of control. From this point of view, it is preferable to use a polymer (a polymer having a polymerizable group and an interactive group).
  • polymer having a polymerizable group and an interactive group a homopolymer copolymer obtained by using a monomer having an interactive group is used, and a polymerizable group includes a bur group, an aryl group, and a (meth) acryl group.
  • Polymers having this polymerizable group and interacting group which are preferably polymers having an ethylenically-added polymerizable unsaturated group (polymerizable group) introduced, such as a polymerizable group at least at the end or side chain of the main chain Those having a polymerizable group in the side chain are preferred.
  • any monomer may be used as long as it is a monomer having the non-dissociative functional group described above. Although it is possible, specific examples include the following.
  • the unit derived from the monomer having the interactive group is a polymerizable group from the viewpoint of interaction formation with the plating catalyst or its precursor.
  • the polymer having an interactive group it is preferably contained in the range of 50 to 95 mol%, more preferably in the range of 40 to 80 mol%.
  • a polymer having a polymerizable group and an interactive group in addition to the above-mentioned monomer having an interactive group, in order to reduce water absorption and improve hydrophobicity.
  • these monomers may be used.
  • the other monomer include a gen-based monomer and an acrylic monomer using a general polymerizable monomer. Of these, unsubstituted alkyl acrylic monomers are preferred. Specifically, tertiary butyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, cyclohexyl acrylate. And benzyl methacrylate are preferably used.
  • Such a polymer having a polymerizable group and an interactive group can be synthesized as follows.
  • a synthesis method i) a monomer having an interactive group and a monomer having a polymerizable group are copolymerized.
  • introducing a double bond introducing a polymerizable group
  • a method in which a monomer having an interactive group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like iii ) A method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.
  • a monomer having an interactive group used for the synthesis of a polymer having a polymerizable group and an interactive group it is possible to use the same monomer as the monomer having an interactive group.
  • Monomers may be used alone or in combination of two or more.
  • Examples of the monomer having a polymerizable group to be copolymerized with the monomer having an interactive group include allyl (meth) acrylate and 2-aryloxetyl methacrylate.
  • Examples of the monomer having a double bond precursor include 2- (3 chloro-1-oxopropoxy) ethyl methacrylate, 2 (3-bromo-1-oxopropoxy) ethyl methacrylate, and the like.
  • the monomer having a polymerizable group examples include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.
  • a polymer having a polymerizable group and an interactive group used in the method for producing a surface metal film material which is one embodiment of the present invention a polymer having a cyano group as an interactive group (hereinafter referred to as “interactive group”). (Referred to as “cyan group-containing polymerizable polymer”).
  • the compound having a polymerizable group and an interactive group such as a cyano group-containing polymerizable polymer in the present invention may have a polar group in addition to the polymerizable group and the interactive group.
  • the polymer layer satisfies the above conditions 1 to 4
  • the polymer has a polar group.
  • a liquid composition containing a compound having a polymerizable group and an interactive group such as a polymer having a polymerizable group and an interactive group. That is, a composition containing a compound having a polymerizable group and an interactive group and a solvent capable of dissolving the compound (preferably a cyan group or O (CH) O
  • n is an integer of 1 to 5
  • a polymer having a polymerizable group a polymer having a polymerizable group
  • the polymer It is preferable to use a polymer layer forming composition of the present invention containing a solvent capable of dissolving
  • the content of the compound having a polymerizable group and an interactive group (for example, a cyano group-containing polymerizable polymer) in the composition is 2% by mass to 50% by mass with respect to the entire composition. Is preferred.
  • the solvent used in the composition is not particularly limited as long as the compound having a polymerizable group and an interactive group, which is a main component of the composition, can be dissolved.
  • a surfactant may be further added to the solvent.
  • Solvents that can be used include, for example, methanolic solvents such as methanol, ethanol, propanol, ethylene glycolenole, glycerin, propylene glycolenomonomethylenoateolate, acids such as acetic acid, acetone, methyl ethyl ketone, and cyclohexanone.
  • amide type, ketone type, nitrile type solvent, carbonate type solvent are preferred, specifically acetone, dimethylacetamide, Methyl ethyl ketone, cyclohexanone, acetonitrile, propionitryl, N-methylpyrrolidone and dimethyl carbonate are preferred.
  • a solvent having a boiling point of 50 to 150 ° C. is preferable from the viewpoint of ease of handling. These solvents may be used alone or in combination.
  • a composition containing a compound having a polymerizable group and an interactive group is applied onto a substrate or a polymerization initiation layer, the substrate or the polymerization initiation layer is coated.
  • a solvent having a solvent absorption of 5 to 25% can be selected. This solvent absorption is determined by the force S obtained from the change in mass when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in the solvent and pulled up after 1000 minutes.
  • a composition containing a compound having a polymerizable group and an interactive group is added to a substrate or a substrate.
  • a solvent in which the swelling ratio of the substrate or the polymerization initiation layer is 10 to 45% may be selected. This swelling ratio can be determined from the change in thickness when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in a solvent and pulled up after 1000 minutes.
  • the surfactant that can be added to the solvent as needed is only required to be soluble in the solvent.
  • a surfactant include sodium n-dodecylbenzenesulfonate.
  • a plasticizer may be added as necessary.
  • Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, jetyl ester, dibutyl ester, di-2-ethyl hexyl ester, dinormaroctyl ester, disononino ester.
  • a polymerization inhibitor may be added to the composition containing a compound having a polymerizable group and an interactive group, if necessary.
  • Polymerization inhibitors that can be used include hydroquinones such as hydroquinone, ditertiary butyl hydroquinone and 2,5-bis (1,1,3,3-tetramethylbutynole) hydroquinone, and phenols such as p-methoxyphenol and phenol.
  • Nitrosamines and catechols can be used.
  • the composition containing a compound having a polymerizable group and an interactive group can be added with a curing agent and / or a curing accelerator to advance the curing of the polymerization initiation layer, if necessary.
  • S can.
  • Known curing agents and curing accelerators can be used.
  • the catalyst type such as a compound having an aliphatic tertiary amine, an aromatic tertiary amine, an imidazole compound, and a Lewis acid complex.
  • those that begin to cure by heat, light, moisture, pressure, acid, base, etc. include: ethylene triamine, triethylenetetramine, tetraethylenepentamine, jetylaminopropylamine, polyamidoamine, mensendiamine, isophoronediamine.
  • curing agents and / or curing accelerators are used in an amount of about 0 to 50% by mass of the remaining non-volatile components from which the solvent has been removed from the viewpoints of solution applicability, adhesion to substrates and adhesive films, and the like.
  • Ability to add S is preferable.
  • the curing agent and / or curing accelerator may be added to the polymerization initiation layer, and in that case, it is preferable that the above range is satisfied by the amount added to the polymerization initiation layer and the total amount added to the polymer layer. Les.
  • rubber components for example, carboxyl terminated butadiene acrylonitrile (CTBN)
  • flame retardants for example, phosphorus flame retardants
  • diluents for example, thixotropic agents, pigments, antifoaming agents
  • a leveling agent, a coupling agent, or the like may be added. Further, these additives may be added to the polymerization initiation layer as necessary.
  • the physical properties of the formed polymer layer for example, thermal expansion coefficient, glass transition Temperature, Young's modulus, Poisson's ratio, breaking stress, yield stress, pyrolysis temperature, etc. can be set optimally. In particular, it is preferable that the breaking stress, yield stress, and thermal decomposition temperature are higher.
  • the obtained polymer layer can be measured for heat durability by a temperature cycle test, a thermal aging test, a reflow test, or the like. For example, with regard to thermal decomposition, if the mass loss when exposed to an environment of 200 ° C for 1 hour is 20% or less, it can be evaluated as having sufficient thermal durability.
  • the coating amount is from the viewpoint of sufficient interaction with the plating catalyst or its precursor.
  • the coating amount in terms of solid content, 0;.! ⁇ 10g / m 2 is preferred tool especially 0. 5 ⁇ 5g / m 2 is not preferable.
  • composition containing a compound having a polymerizable group and an interactive group When a composition containing a compound having a polymerizable group and an interactive group is applied on a substrate and dried to form a layer containing a compound having a polymerizable group and an interactive group, Leave between 20 and 40 ° C for 0.5 to 2 hours between application and drying. The solvent may be removed.
  • Examples of a method for applying energy to the substrate surface include a method using radiation irradiation such as heating and exposure.
  • the method include UV lamp, irradiation with visible light, etc., heating using a hot plate and the like.
  • Examples of the light source used in the method include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far-infrared rays.
  • g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) can be used.
  • Specific examples of specific modes that are generally used include direct image recording with a thermal recording head, scanning exposure with an infrared laser, high illumination flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • the time required for energy application varies depending on the amount of the graft polymer produced and the light source, and is usually between 10 seconds and 5 hours.
  • the exposure power is 10 mj / cm to 5000 mj / in order to facilitate the progress of graft polymerization and to suppress the decomposition of the generated graft polymer. More preferably in the range of cm, 50 mj / cm 2
  • step (al) described above it is possible to form a polymer layer (graft polymer layer) made of a graft polymer having an interactive group on the substrate.
  • the obtained polymer layer strength For example, when the decomposition of the polymerizable group portion is 50% or less when added to an alkaline solution at pH 12 and stirred for 1 hour, the polymer layer has high alkalinity. Cleaning with a solution can be performed.
  • a polymer layer made of a polymer having a cyano group and directly chemically bonded to the substrate is formed.
  • This step is a method similar to the method described in step (al) except that a compound having a polymerizable group and a cyano group is used as the compound having a polymerizable group and an interactive group in step (al) described above.
  • a compound having a polymerizable group and a cyano group is used as the compound having a polymerizable group and an interactive group in step (al) described above.
  • the polymer constituting the polymer layer obtained in this step has a cyano group as a functional group that forms an interaction with the plating catalyst or its precursor.
  • this cyano group has a high adsorption ability to a plating catalyst having a high polarity, but it does not have a high water absorption and hydrophilicity like a dissociative polar group (hydrophilic group).
  • the polymer layer composed of the graft polymer having a cyano group has low water absorption and high hydrophobicity.
  • a catalyst or a precursor thereof is added to the polymer layer formed in the step (al) or (al ′).
  • an interactive group (cyan group) possessed by the draft polymer that constitutes the polymer layer is given according to its function, and attaches (adsorbs) the catalyst or precursor thereof.
  • examples of the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in the plating step (a3) described later. Therefore, the plating catalyst or its precursor is determined by (a3) the type of plating in the plating step.
  • the plating catalyst or its precursor used in this step is preferably an electroless plating catalyst or its precursor.
  • Any electroless catalyst used in the present invention can be used as long as it becomes an active nucleus during electroless plating.
  • Examples thereof include metals having catalytic ability for autocatalytic reduction reactions (known as metals capable of electroless plating with a low N-beam ionization tendency).
  • Specific examples include forces S such as Pd, Ag, Cu, Ni, Al, Fe, and Co.
  • forces S such as Pd, Ag, Cu, Ni, Al, Fe, and Co.
  • those capable of multidentate coordination are preferable.
  • functional groups that can be coordinated Pd is preferred because of the number of types and high catalytic ability.
  • This electroless plating catalyst may be used as a metal colloid.
  • metal colloids In general, metal colloids
  • It can be prepared by reducing a metal ion in a solution containing a charged surfactant or a charged protective agent.
  • the charge of the metal colloid can be controlled by the surfactant or protective agent used here.
  • Electroless plating catalyst precursor [0141] Electroless plating catalyst precursor
  • the electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can be a nonelectrolytic plating catalyst by a chemical reaction.
  • the metal ions of the metals mentioned above as the electroless plating catalyst are mainly used.
  • the metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction.
  • the metal ion, which is an electroless plating catalyst precursor may be applied to the polymer layer and then converted into a zero-valent metal by a reduction reaction before immersion in the electroless plating bath to form an electroless plating catalyst. Then, it may be immersed in an electroless plating bath as the electroless plating catalyst precursor, and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.
  • the metal ion which is an electroless plating precursor, is applied onto the polymer layer using a metal salt.
  • the metal salt used is not particularly limited as long as it is dissolved in an appropriate solvent and can be dissociated into a metal ion and a base (anion). Specific examples include M (NO), M
  • the thing which said metal salt dissociated can be used suitably.
  • Specific examples include Ag ions, Cu ions, A1 ions, Ni ions, Co ions, Fe ions, and Pd ions.
  • those capable of multidentate coordination are preferable.
  • Pd ions are preferred in terms of the number of types of functional groups capable of coordination and the catalytic ability.
  • a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a metal is used.
  • the salt was dissolved in an appropriate solvent to prepare a solution containing dissociated metal ions, and the dispersion or solution was applied onto the polymer layer, or the polymer layer was formed in the dispersion or solution. Soak the substrate.
  • a composition containing a compound having a polymerizable group and an interactive group (cyan group) is brought into contact, and a method of adding an electroless plating catalyst or a precursor thereof to the composition may be used.
  • a surface graft polymerization method is applied by contacting a composition containing a compound having a polymerizable group and an interactive group (cyan group) with an electroless plating catalyst or a precursor thereof on a substrate.
  • the (al) or (al ′) step and the (a2) step in the present invention can be performed in one step.
  • the interaction group (Cyan group) in the polymer layer interacts with an intermolecular force such as van der Waals force.
  • the electroless plating catalyst or its precursor can be adsorbed by utilizing the interaction due to the coordinate bond by the lone pair of electrons.
  • the metal concentration in the dispersion, solution, or composition, or the metal ion concentration in the solution may be in the range of 0.00; The range of 0.005 to 30% by mass is more preferable. Further, the contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.
  • a zero-valent metal can be used as a catalyst used for direct electroplating without performing electroless plating on the polymer layer in the step (a3) described later.
  • the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among them, those capable of multidentate coordination are preferable.
  • Pd, Ag, and Cu are preferred because of their high adsorptive (adhesive) property to interactive groups (cyan groups) and high catalytic ability.
  • the interaction group (cyan group) in the polymer layer is identified.
  • An interaction can be formed between the catalyst and its precursor.
  • a plating film is formed by plating the polymer layer to which the electroless plating catalyst or its precursor is applied.
  • the formed adhesive film has excellent conductivity and adhesion.
  • step (a2) depending on the function of the plating catalyst or its precursor that has formed an interaction with the polymer layer. Can be selected.
  • electroplating or electroless plating can be applied to the polymer layer to which the plating catalyst or its precursor has been applied.
  • electroless plating is preferably performed from the viewpoint of the formation of a hybrid structure expressed in the polymer layer and the improvement of adhesion.
  • electrical plating is further performed after electroless plating.
  • Electroless plating refers to the operation of depositing metal by chemical reaction using a solution in which the metal ions to be deposited as a plating solution are dissolved.
  • the electroless plating in this process is performed, for example, by rinsing a substrate to which an electroless plating catalyst has been added to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath.
  • the electroless bath used is the power of using a generally known electroless bath.
  • the catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to a zerovalent metal is dissolved, and the concentration of the precursor with respect to the entire liquid is
  • reducing agents include boron reducing agents such as sodium borohydride and dimethylolamine borane, and reducing agents such as formaldehyde and hypophosphorous acid.
  • the composition of a general electroless plating bath includes, in addition to the solvent, 1. metal ions for plating, 2. reducing agents, 3. additives that improve the stability of metal ions (stabilizers) Is mainly included.
  • the plating bath may contain known additives such as a plating bath stabilizer.
  • an organic solvent having a high affinity for a highly hydrophobic polymer layer with low water absorption (a polymer layer that satisfies all of the above conditions 1 to 4) is used.
  • Power of inclusion S is preferable.
  • the selection and content of the organic solvent may be adjusted according to the physical properties of the polymer layer. In particular, the larger the saturated water absorption in the condition 1 of the polymer layer, the smaller the organic solvent content is preferred. Specifically, it is as follows.
  • the content of the organic solvent in the total solution of the plating bath is 20 to 80% by mass.
  • the rate is 0.5 to 5% by mass
  • the content of the organic solvent in the total solvent of the plating bath is 10 to 80% by mass. S is preferable.
  • the saturated water absorption is 5 to 10% by mass.
  • the content of the organic solvent in the total solvent of the plating bath is 0 to 60% by mass. The amount is preferably 0 to 45% by mass.
  • the organic solvent used in the plating bath needs to be a solvent that can be used in water. From this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.
  • ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.
  • Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath. Of these, from the viewpoint of conductivity, copper and gold are used. Especially preferred.
  • a copper electroless bath may contain CuSO as the copper salt, HCOH as the reducing agent, and copper ion as the additive.
  • the metal bath used for electroless plating of CoNiP includes cobalt sulfate, nickel sulfate as a metal salt, sodium hypophosphite as a reducing agent, sodium malonate, malic acid as a complexing agent. Contains sodium and sodium succinate.
  • palladium electroless baths include (Pd (NH)) C1 as metal ions, NH as a reducing agent,
  • the film thickness of the electroless plating formed in this way can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. it can. From the viewpoint of conductivity, the film thickness is preferably 0.5 m or more, more preferably 3 ⁇ 111 or more.
  • the immersion time in the plating bath is preferably about 1 minute to 6 hours, more preferably about 1 minute to 3 hours.
  • the electroless plating film obtained as described above is obtained by cross-sectional observation with a scanning electron microscope (SEM) in the polymer layer. It was confirmed that the fine particles made of the above were dispersed at a high density, and that the plated metal was further deposited on the polymer layer. Since the interface between the substrate and the plating film is a hybrid state of polymer and fine particles, the interface between the substrate (organic component) and the inorganic material (catalyst metal or metal) is smooth (for example, the unevenness difference is 500 nm or less) Even so, the adhesion is good.
  • SEM scanning electron microscope
  • step (a2) if the catalyst or its precursor applied in step (a2) has a function as an electrode, the polymer layer to which the catalyst or its precursor is applied On the other hand, it is possible to carry out electrical plating.
  • the metal film can be formed with a thickness according to the purpose, and therefore, the metal film of the present invention is suitable for various applications.
  • a method of electroplating in the present invention a conventionally known method can be used.
  • metals used for electroplating in this step include copper, chromium, lead, nickel gnole, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is more preferable.
  • the thickness of the metal film obtained by electroplating varies depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath or the current density.
  • the film thickness when used for general electric wiring is preferably 0.5 m or more, more preferably 3 m or more from the viewpoint of conductivity.
  • the metal or metal salt derived from the above-described plating catalyst, plating catalyst precursor, and / or metal deposited in the polymer layer by electroless plating is fractal in the layer.
  • the adhesion between the metal film and the polymer layer can be further improved.
  • the amount of metal present in the polymer layer is 5 to 50% by area when the cross section of the substrate is photographed with a metal microscope, and the proportion of the metal in the region from the outermost surface of the polymer layer to a depth of 0.5 mm is Further, when the arithmetic average roughness Ra (ISO 4288 (1996)) between the polymer layer and the metal interface is 0.05 ⁇ m to 0.5 m, a stronger adhesion force is expressed.
  • Ra arithmetic average roughness
  • the surface metal film material of the present invention can be obtained. If the third method for producing a surface metal film material of the present invention is applied, a surface metal film material having a metal film formed on both surfaces can be obtained.
  • the surface metal film material obtained by the method for producing a surface metal film material of the present invention has an effect that there is little fluctuation in the adhesion of the metal film even under high temperature and high humidity.
  • This surface The metal film material can be applied to various uses such as an electromagnetic wave prevention film, a coating film, a two-layer CCL (Copper Clad Laminate) material, and an electric wiring material.
  • the method for producing the metal pattern material of the present invention includes a step of etching the plating film of the surface metal film material of the present invention obtained through the steps (al) to (a3) into a pattern.
  • the padding film (metal film) formed in the step (a3) is etched into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the cover film formed on the entire substrate surface by etching.
  • Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.
  • a dry film resist layer is provided on the deposited film, the same pattern as the metal pattern is formed by pattern exposure and development, and plating is performed with an etching solution using the dry film resist pattern as a mask.
  • This is a method of removing a film and forming a metal pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like materials can be used.
  • an etching method any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In view of the operation, wet etching is preferable because the apparatus is simple. Examples of usable etching solutions include aqueous solutions of cupric chloride and ferric chloride.
  • the semi-additive method is a method in which a dry film resist layer is provided on a coating film to be formed, and the same pattern as a non-metallic pattern portion is formed by pattern exposure and development, and the dry film resist pattern is used as a mask.
  • This is a method of forming a metal pattern by performing electrical etching, removing the dry film resist pattern, performing quick etching, and removing the plating film in a pattern.
  • materials such as dry film resist and etching solution, the same materials as in the subtractive method can be used.
  • the method described above can be used as the electroplating method.
  • a metal pattern having a desired metal pattern is obtained through the above steps (al) to (a4).
  • the material is made.
  • the metal pattern material is obtained.
  • the energy applied when forming the polymer layer may be changed into a pattern. Then, a pattern-like polymer layer can be formed by removing a portion to which energy is not applied by development.
  • the developing method is carried out by immersing a material used for forming a polymer layer such as a compound having a polymerizable group and an interactive group (cyan group) in a solvent capable of dissolving.
  • the immersion time is preferably in the range of 1 minute to 30 minutes.
  • the polymer layer (al) or (al ′) is directly patterned by a known coating method such as gravure printing, ink jet method, spray coating method using a mask, and then given energy, and then developed. You may form by.
  • Steps (a2) and (a3) for forming a plating film on the polymer layer formed with the pattern are the same as those described above.
  • the metal pattern material of the present invention is obtained by the above-described method for producing a metal pattern material of the present invention.
  • the polymer layer constituting the obtained metal pattern material has low water absorption and high hydrophobicity, the exposed portion of the polymer layer (the metal pattern non-formation region) is excellent in insulation reliability. .
  • the metal pattern material of the present invention preferably has a metal film (plating film) provided on the entire surface or locally on the substrate having a surface unevenness difference of 500 nm or less (preferably 100 ⁇ m or less).
  • the adhesion between the substrate and the metal pattern is preferably 0.2 kN / m or more. That is, the substrate surface is smooth, but the adhesion between the substrate and the metal pattern is excellent.
  • the unevenness difference on the substrate surface is obtained by cutting the substrate perpendicularly to the substrate surface and It is the value measured by observing with SEM.
  • Rz of the substrate surface measured according to ISO 4287 (1997) that is, “the average value of the Z data of the highest to fifth peaks and the lowest to fifth valleys on the specified surface.
  • the “difference from the average value of the bottom” is preferably 500 nm or less.
  • the adhesion value between the substrate and the metal film is determined by bonding a copper plate (thickness: 0.1 mm) to the surface of the metal film (metal pattern) with an epoxy adhesive (trade name: Araldite, manufactured by Ciba Geigy). After drying at 140 ° C for 4 hours, perform a 90-degree peeling experiment based on JIS C 6481 (a known test method for copper-clad laminates for printed wiring boards in accordance with IEC 60249-1 (1982)), or This is a straight line obtained by directly peeling off the end of the metal film itself and conducting a 90-degree peeling test based on JIS C 6481.
  • JIS C 6481 a known test method for copper-clad laminates for printed wiring boards in accordance with IEC 60249-1 (1982)
  • the metal pattern material obtained by the method for producing a metal pattern material of the present invention includes, for example, a semiconductor chip, various electric wiring boards, FPC (Flexible Print Circuit), COF (Chip On Film), TAB (Tape Automated). Bonding), antenna, multilayer spring board, mother board, etc.
  • FPC Flexible Print Circuit
  • COF Chip On Film
  • TAB Tape Automated
  • Bonding antenna
  • multilayer spring board mother board, etc.
  • the novel polymer provided as one embodiment of the present invention is a copolymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2).
  • the novel polymer is one of the preferred examples of the above-mentioned cyano group-containing polymerizable polymer used in the method for producing a surface metal film material which is one embodiment of the present invention.
  • the novel polymer will be described in detail by appropriately referring to a “nitrile group-containing polymerizable polymer”.
  • examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Includes a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.
  • R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 3 is preferably a hydrogen atom.
  • R 4 is preferably a hydrogen atom.
  • R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic group.
  • Family carbonization A hydrogen group is mentioned.
  • a substituted or unsubstituted aliphatic hydrocarbon group a methylene group, an ethylene group, a propylene group, a butylene group, or these groups are substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like.
  • the ones made are preferred.
  • the substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.
  • one (CH 3) — (n is an integer of 1 to 3) is preferable, and one CH— is more preferable.
  • L 1 is preferably a divalent organic group having a urethane bond or a urea bond, and even more preferably a divalent organic group having a urethane bond. ! ⁇ 9 are preferred.
  • the total number of carbon atoms of L 1 means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 1.
  • L 1 is preferably a structure represented by the following formula (11) or formula (12).
  • Rb are each independently two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom.
  • Preferred examples of the divalent organic group to be formed include substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group, ethylene oxide group, diethylene oxide group, triethylene oxide group, tetra Examples include an ethylene oxide group, a dipropylene oxide group, a tripropylene oxide group, and a tetrapropylene oxide group.
  • L 2 represents a linear, branched, or cyclic alkylene group, an aromatic group, or a combination thereof. It's preferable to have a combined group! / The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L 2 preferably has a total carbon number of 1 to 15 and is particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L 2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 2.
  • Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, etc. Includes a combination of these.
  • nitrile group-containing polymerizable polymer of the present invention include those in which the unit represented by the formula (1) is a unit represented by the following formula (3).
  • R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond, a substituted or unsubstituted divalent organic group.
  • Group represents an ester group, an amide group, or an ether group, W represents an oxygen atom, or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom, or an unsubstituted one having 1 to 5 carbon atoms.
  • L 1 represents a substituted or unsubstituted divalent organic group.
  • Equation (3) the formula (1) have the same meanings as R 1 and R 2 in, and so are the preferable examples.
  • Z in the formula (3) has the same meaning as Z in the formula (1), and preferred examples thereof are also the same.
  • L 1 in the formula (3) has the same meaning as L 1 in the formula (1), and preferred examples thereof are also the same.
  • the nitrile group-containing polymerizable polymer of the present invention includes a unit represented by the formula (3).
  • the unit is represented by the following formula (4)! /.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group
  • V and W each independently represent an oxygen atom or NR
  • R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms.
  • L 1 represents a substituted or unsubstituted divalent divalent group. Represents an organic group.
  • Equation (4) the formula (1) have the same meanings as R 1 and R 2 in, and so are the preferable examples.
  • L 1 in the formula (4) has the same meaning as L 1 in the formula (1), and preferred examples thereof are also the same.
  • W is preferably an oxygen atom.
  • L 1 is a divalent alkylene group, or a divalent group having a urethane bond, preferably a urethane bond or a divalent organic group having a urea bond.
  • organic groups are more preferable, those having 1 to 9 carbon atoms are particularly preferable.
  • the nitrile group-containing polymerizable polymer of the present invention includes a unit represented by the above formula (2). It is preferably a unit represented by the following formula (5)
  • R 5 represents a hydrogen atom or a substituted or unsubstituted alkyl group
  • U represents an oxygen atom, or NR '(where R' is a hydrogen atom or an alkyl group) And preferably represents a hydrogen atom or an unsubstituted alkyl group having 15 carbon atoms
  • L 2 represents a substituted or unsubstituted divalent organic group.
  • R 5 in formula (5) has the same meaning as R 1 and R 2 in formula (1), and is preferably a hydrogen atom.
  • L 2 in the formula (5) has the same meaning as L 2 in the formula (1), and a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these Is preferred.
  • the organic group has a total carbon number of 1 to 10;
  • Another preferred embodiment is one in which the linking site with the cyan group in L 2 in formula (5) is a divalent organic group having an aromatic group. More preferably, the group has a total carbon number of 6 to 15;
  • the nitrile group-containing polymerizable polymer of the present invention comprises units represented by the above formulas (1) to (5), and has a polymerizable group and a nitrile group side by side. Is a polymer in the chain
  • This nitrile group-containing polymerizable polymer can be synthesized, for example, as follows.
  • Examples of the polymerization reaction when synthesizing the nitrile group-containing polymerizable polymer of the present invention include radical polymerization, cationic polymerization, and anion polymerization. From the viewpoint of reaction control, it is preferable to use radical polymerization or cationic polymerization.
  • the nitrile group-containing polymerizable polymer of the present invention includes: 1) the case where the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain, and 2) the formation of the polymer main chain.
  • the synthesis method differs depending on whether the polymerization form is the same as the polymerization form of the polymerizable group introduced into the side chain.
  • examples of the monomer used in an embodiment in which the polymer main chain is formed by cationic polymerization and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization include the following compounds.
  • Monomers used to form the polymerizable group-containing unit used in the present embodiment include bur (meth) acrylate, allyl (meth) acrylate, 4- (meth) attaroyl butyl butyl ether, 2 (Meth) Ataliloyl tert-butyl ether, 3 (Meth) Atalloy Rolepronovininoreatenore, (Meth) Atalloyroxydiethyleneglycolenorevininoreate Tenole, (Meth) Atalloyrooxytriethyleneglycololevininoateoret, (Meth) Atariroinole 1st terpioneer, 1— (Meth) Atariloy oxyl 2-methyl 2-propene, 1— (Meth) Atalloy oxynoxy 3 Methyl 3 butene, 3 Methylene -1- 2-(Meth) Atearliesturooxy Atalylate, 2- (bromomethyl) acrylic acid butyl, 2-ary
  • Monomers used to form the nitrile group-containing unit used in this embodiment include 2 cyanoethyl butyl ether, cyanomethyl butyl ether, 3 cyanopropyl pyrulb ether, and 4- cyanobutyl butyl ether.
  • Polymerization methods include those described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 4 ( ⁇ 74), and “Experimental Methods for Polymer Synthesis” written by Takatsu Otsu, Chapter 7 ( ⁇ 195).
  • Cationic polymerization can be used.
  • examples of initiators that can be used in cationic polymerization include proton acids, metal halides, organometallic compounds, organic salts, metal oxides, solid acids, and halogens. Of these, metal halides and organometallic compounds are active. Is preferable because it is a large initiator having a high molecular weight.
  • boron trifluoride examples include boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, tin bromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, and chloride.
  • Examples include iron, dichloroethylaluminum, chlorojetylaluminum, dichloromethylaluminum, chlorodimethylaluminum, trimethylaluminum, trimethylzinc, and methyldarinia.
  • the following compounds may be used as the monomer used in an embodiment in which the polymer main chain is formed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.
  • Examples of monomers used to form the nitrile group-containing unit used in this embodiment include cyanomethyl (meth) acrylate, 2- cyanoethyl (meth) acrylate, 3- til (meth) acrylate, 4-cyano butyl ( (Meth) atarylate, 5—cyanopentyl (meth) atallylate, 6—cyanhexyl (meth) acrylate, 7—cyanhexyl (meth) acrylate, 8 cyanhexyl (meth) acrylate, 2 cyanoethyl ( 3 (bromomethyl) acrylate), 2 cyanoethyl (3- (hydroxymethyl) acrylate), p cyanophenyl (meth) acrylate, o cyanophenyl (meth) acrylate, m cyanophenyl (meth) acrylate, 5 ( Meta) Atari Roy Roux 2 Carbonitorilonorbornene, 6— (Meth) Atarylloyl—
  • a monomer having a structure in which a part of hydrogen of the monomer is substituted with a hydroxyl group, an alkoxy group, a halogen, a cyan group, or the like can also be used.
  • Polymerization methods include those described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu, Chapter 5 (pl25).
  • a radical polymerization method can be used.
  • radical polymerization initiators include high-temperature initiators that require heating of 100 ° C or higher, normal initiators that start with heating at 40 to 100 ° C, and redox initiators that start at extremely low temperatures. However, an initiator is usually preferred because of the stability of the initiator and ease of handling of the polymerization reaction.
  • normal initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, and azovir-1,4 dimethylvaleronitrile.
  • the same monomer as the monomer used for forming the nitrile group-containing unit mentioned in the embodiment 1-1) is used as the monomer having a nitrile group.
  • a polymer having a nitrile group is synthesized in advance, and then the polymer and a compound having a cationic polymerizable group (hereinafter referred to as “ This is referred to as a “reactive compound”. And a method in which a cationically polymerizable group is introduced into the side chain.
  • the polymer having a nitrile group preferably has a reactive group as shown below for reaction with the reactive compound.
  • the polymer having a nitrile group and the reactive compound are preferably selected as appropriate so as to have the following combination of functional groups.
  • the reactive compound examples include allylic alcohol, 4-hydroxybutane vinylenoleate, 2-hydroxyethanevininoreatenore, 3-hydroxypropane vinylenoleate, hydroxytriethyleneglycolenolebi. Mention may be made of ninoleatenore, 1st tenolepioneore, 2-methyl-2-propenol, 3-methyl-3-butenol, 3-methylene-2-hydroxy-norbornane, p- (chloromethyl) styrene.
  • synthesis methods include i) a method of copolymerizing a monomer having a nitrile group and a monomer having a polymerizable group, and ii) a monomer having a nitrile group and a double bond.
  • An introduction method (introducing a polymerizable group) can be mentioned.
  • a polymer having a tolyl group is reacted with a monomer having a polymerizable group to introduce a polymerizable group.
  • Examples of the monomer having a polymerizable group used in the synthesis method i) include a aryl (meth)
  • Examples include talirate and the following compounds.
  • Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula ⁇ .
  • Yukidan A is having a polymerizable group
  • R 1 ⁇ ! T is independently a hydrogen atom or a monovalent organic group
  • B and C are leaving groups that are removed by a leaving reaction
  • the term “separating reaction” here refers to C being extracted by the action of a base.
  • B is desorbed.
  • B is preferred as anion and C as a cation! /.
  • Preferable examples of the base used in the above elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds.
  • Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, carbonate Sodium, potassium hydrogen carbonate, sodium hydrogen carbonate, etc. are mentioned.
  • the organic amine compound include trimethylamine, rietinolemin, jetinoremethinolemine, ⁇ lif ⁇ noremine, ⁇ liisof ⁇ nolemine, ⁇ hexylamine, trioctinoleamine, N, N dimethyl Cyclohexylamine, N, N- ethynolecyclohexenoleamine, N methinoresincyclohexenoleamine, N ethenoresic mouth hexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methinoleviperidine, 2, 2 , 6, 6—tetramethinorebiperidine, piperazine, 1, 4 Dimethinoleviperazine, quinutaridin, 1,4-diazabicyclo [2, 2, 2] octane, hexamethylenetetramine, monoreforin, 4-methinoremonore
  • Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, prono.
  • the amount of the base used may be less than or equal to the amount of the specific functional group (leaving group represented by B or C) in the compound. Also good.
  • an excess base it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.
  • the polymer having a nitrile group used in the synthesis method of iii) includes a monomer used for forming the nitrile group-containing unit mentioned in the above embodiment 1 2) and a double bond introduction. It is synthesized by radical polymerization of a monomer having a reactive group.
  • Examples of the monomer having a reactive group for introducing a double bond include a monomer having a reactive carboxyl group, a hydroxyl group, an epoxy group, or an isocyanate group as a reactive group.
  • carboxyl group-containing monomers examples include (meth) acrylic acid, itaconic acid, benzoic acid bur; Alonitas M-5300, M-5400, M-5600 manufactured by Toagosei (all trade names) ); Mitsubishi Rayon Acrylic Esters PA, HH (all trade names); Kyoeisha Chemical Light Atylate HOA—HH (all trade names); Nakamura Chemical NK Esters SA, A— SA (all trade names) Etc.
  • hydroxyl group-containing monomers examples include 2 hydroxyethyl (meth) acrylate, 4 hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (Meth) Atarylloyl 3-hydroxy-1-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl) (meth) atalylate, 2- (hydroxymethyl) methyl ester of (meth) atalylate, 3 chloro-2-hydroxypropyl (Meth) Athalylate, 3,5-Dihydroxypentyl (Meth) Atalylate, 1-Hydroxymethyl-4 (Meth) Ataliloylmethyl-cyclohexane, 2 Hydroxy-3 Hue
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, Cyclomers A and M (both trade names) manufactured by Daicel Chemical Industries, and the like.
  • Examples of monomers having an isocyanate group include power lenses AOI and MOI (both trade names) manufactured by Showa Denko.
  • the polymer having a nitrile group used in the synthesis method iii) may further contain a third copolymer component.
  • the monomer having a polymerizable group to be reacted with the polymer having a nitrile group varies depending on the kind of the reactive group in the polymer having a nitrile group.
  • Monomers having the following combinations of functional groups can be used.
  • (polymer reactive group, monomer functional group) (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide) , (Hydroxyl group, carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, benzyl halide) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), (epoxy group, carboxyl group) ) Etc. Power S.
  • a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group are used, and the isocyanate group is added to the hydroxyl group. and forming a urethane bond in L 1 by.
  • the unit type containing nitrile group described in the above embodiment 1-2 examples thereof include copolymers of monomers used for the formation and the following hydroxyl group-containing (meth) acrylates.
  • hydroxyl group-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (meth) atteroyl 1-3 hydroxy 1 adamantane, hydroxymethinole ( (Meth) atalinoleamide, 2- (hydroxymethyl) (meth) atalylate, 2 (hydroxymethyl) methyl ester of (meth) atalylate, 3 chloro-2 hydroxypropyl (meth) atalylate, 3, 5 dihydroxypentyl (meta) ) Atarylate, 1-Hydroxymethylenole 4 (Meth) Atalylurolemethinole cyclohexane, 2-Hydroxy 3 Phenoxypropyl (meth) acrylate, 1-Methyl-2- Atalylyloxypropyl phthalate, 2 —Atariloylokichetil 2-hydroxyethyl phthalate 1-Methinore 2-
  • the polymer having a hydroxyl group in the side chain used in the polymer synthesis method of the present invention may further contain a third copolymer component.
  • a bifunctional acrylate is produced as a by-product when synthesizing a hydroxy group-containing (meth) acrylate as a raw material. It is preferable to use a polymer synthesized using a raw material from which the water has been removed. As the purification method, distillation and column purification are preferred. More preferably, it is synthesized using a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the following steps (1) to (4).
  • the mixture used in the step (1) is composed of a hydroxyl group-containing (meth) atrelate and a bifunctional atallylate that is an impurity by-produced when the hydroxyl group-containing (meth) acrylate is synthesized. It corresponds to a general commercial product of hydroxyl group-containing (meth) acrylate.
  • this commercial product (mixture) is dissolved in water to obtain an aqueous solution.
  • a first organic solvent that separates from water is added to the aqueous solution obtained in the step (1).
  • the first organic solvent used here include ethyl acetate, jet ether, benzene, toluene and the like.
  • the layer (oil layer) containing the first organic solvent and the bifunctional acrylate is separated from the aqueous solution (aqueous layer).
  • step (3) a compound having higher water solubility than the hydroxyl group-containing (meth) acrylate is dissolved in the water layer separated from the oil layer in the step (2).
  • examples of compounds include alkali metal salts such as sodium chloride and potassium chloride, alkaline earth metals such as magnesium sulfate and calcium sulfate An inorganic salt such as a salt is used.
  • a second organic solvent is added to the aqueous layer to extract hydroxyl group-containing (meth) atalylate, followed by concentration.
  • Examples of the second organic solvent used here include ethyl acetate, jetyl ether, benzene, toluene and the like. This second organic solvent may be the same as or different from the first organic solvent described above.
  • Concentration in the step (4) includes drying with anhydrous magnesium sulfate and distillation under reduced pressure. Used.
  • An isolate containing a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the steps (1) to (4) described above contains a bifunctional acrylate in a total mass of 0.1. It is preferable to contain in the range below mass%. That is, through the steps (1) to (4), the bifunctional acrylate is removed from the mixture, and the hydroxyl group-containing (meth) acrylate is purified.
  • a more preferable range of the content of the bifunctional attalylate is 0.05% by mass or less based on the total mass of the isolate.
  • the bifunctional acrylate which is an impurity is less likely to affect the polymerization reaction. Therefore, a nitrile group-containing polymerizable compound having a weight average molecular weight of S20000 or more is required. Polymers can be synthesized.
  • hydroxy group-containing (meth) acrylate used in the step (1) when synthesizing a polymer having a hydroxyl group in the side chain used in the polymer synthesis method of the present invention described above, It is possible to use the ones listed as hydroxyl group-containing (meth) acrylates used. Among these, from the viewpoint of reactivity to isocyanate, a monomer having a primary hydroxyl group is preferred, and from the viewpoint of increasing the ratio of polymerizable groups per unit weight of the polymer, a hydroxy group having a molecular weight of 100 to 250 is preferred. Contained (meth) acrylate is preferred.
  • 2-atallyloyloxychetyl isocyanate (trade name: Power Lens A OI, Showa) Electric Works Co., Ltd.), 2-methacryloxy isocyanate (trade name: Power Lens MOI, Showa Denko Co., Ltd.) and the like.
  • the solvent used in the method for synthesizing the polymer of the present invention is preferably one having an SP value (calculated by the Okitsu method) of 20 to 23 MPa 1/2.
  • SP value calculated by the Okitsu method
  • ethylene glycol Diacetate Diethylene glycol diacetate, Propylene glycol diacetate, Methyl acetate acetate, Ethyl acetate acetate, 1,2,3-Triacetoxy-propane, Cyclohexanone, 2- (1-cyclohexenole) cyclohexanone, Propioni Tolyl, N-Methylpyrrolidone, Dimethylacetamide, Acetylacetone, Acetophenone, Triacetin, 1,4-di And oxane, dimethyl carbonate, and the like.
  • an ester solvent is more preferable, and a diacetate solvent such as ethylene glycol diacetate and diethylene glycol diacetate, and dimethyl carbonate are more preferable.
  • the SP value of the solvent in the present invention is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula.
  • a F is a value described in the literature.
  • the ratio of the polymerizable group-containing unit and the nitrile group-containing unit is in the following range with respect to the entire copolysynthesis component. It is preferable.
  • the polymerizable group-containing unit is contained in an amount of 5 to 50 mol% with respect to the entire copolymerization component, and more preferably 5 to 40 mol%. If it is less than 5 mol%, the reactivity (curability and polymerizability) is lowered, and if it is more than 50 mol%, it tends to gel during synthesis and is difficult to synthesize. Also, the nitrile group-containing unit should be included in the range of 10 to 95 mol%, preferably in the range of 5 to 95 mol% with respect to the entire copolymerization component, from the viewpoint of adsorptivity to the plating catalyst and the like. Is more preferable.
  • the nitrile group-containing polymerizable polymer of the present invention may contain other units in addition to the nitrile group-containing unit and the polymerizable group-containing unit.
  • the monomer used to form the other unit a monomer that can be used can be used as long as the effects of the present invention are not impaired.
  • monomers used to form units other than the nitrile group-containing unit and the polymerizable group-containing unit described above include ethyl (meth) when the polymer main chain is formed by radical polymerization.
  • Atarylate butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate,
  • Unsubstituted (meth) acrylic acid esteres such as benzyl (meth) acrylate and stearyl (meth) acrylate, 2, 2, 2 Trifnore loyetinore (meth) acrylate, 3, 3, 3 Trifonole propyl (meta)
  • Atalylates halogen-substituted (meth) acrylic esters such as 2-cycloethyl (meth) acrylate, 2- (meth) acryloyllochichetyltrimethylam
  • the macromonomer obtained using the monomer of the said description can also be used.
  • the polymer main chain is formed by cationic polymerization, ethyl butyl ether, butyl vinyl enoate, isobutino levino ree tenole, cyclohexeno levino ree tenole, ethylen glycino levino ree tenole, di ( (Ethylene glycolenole), vinylenoreethenore, 1,4 butanediolenolevininoleethenore, 2-chloroethinorevininoreethenore, 2-ethenorehexinolevininoreethenore, vinylinole acetate, 2-vininoreoxytetrahydropyran, Use can be made of vinyl ethers such as vinylolene benzoate and butyl butyrate, styrenes such as styrene, p-chlorostyrene, and p
  • the weight average molecular weight of the nitrile group-containing polymerizable polymer of the present invention is preferably 1000 or more and 700,000 or less, more preferably 2000 or more and 200,000 or less.
  • the weight average molecular weight of the nitrile group-containing polymerizable polymer of the present invention is preferably 20000 or more.
  • the polymerization degree of the nitrile group-containing polymerizable polymer of the present invention is more preferably a 20-mer or more, preferably a 10-mer or more.
  • 700-mer or less is preferable 3000-mer or less is more preferable 2000-mer or less is more preferable
  • 1000-mer or less is particularly preferable.
  • acrylic acid and 2-cyanoethyl acrylate are dissolved in, for example, N-methylpyrrolidone, and the polymerization initiator is, for example, azoisobut Perform radical polymerization using tyronitrile (AIBN), and then add glycidyl methacrylate with a catalyst such as benzyltrityl ammonium chloride and a polymerization inhibitor such as tertiary butyl nodroquinone. It is the power of synthesis by reacting.
  • AIBN tyronitrile
  • the following monomers and p-cyanobenzatylate are dissolved in a solvent such as N, N-dimethylacrylamide, and dimethyl azobutyrate is used. It can be synthesized by performing radical polymerization using a suitable polymerization initiator and then dehydrochlorinating using a base such as triethylamine.
  • the nitrile group-containing polymerizable polymer of the present invention is, for example, added to an alkaline solution having a pH of 12 and stirred for 1 hour when the decomposition of the polymerizable group site is 50% or less. Can be washed with a highly alkaline solution.
  • the nitrile group-containing polymerizable polymer of the present invention is a copolymer of a unit having a nitrile group and a unit having a polymerizable group, by changing the ratio of the units, it can be applied to a metal such as a plating catalyst.
  • a metal such as a plating catalyst.
  • the ability to control adsorption and polymerization (reactivity) can be controlled.
  • Such a nitrile group-containing polymerizable polymer of the present invention is not only a photocurable resin composition but also a molding material, a coating material, a surface modifying material, and a substrate material in the electronic field, the mechanical field, the food field, and the construction field. It can be used in the field and the automobile field.
  • the nitrile group-containing polymerizable polymer of the present invention forms a plating film because it is hydrophobic and has excellent adsorptivity and polymerizability to the plating catalyst. It is preferable to be used as a surface treatment material.
  • the nitrile group-containing polymerizable polymer of the present invention is directly adsorbed onto a desired substrate using a surface graft polymerization method or the like, thereby adsorbing to a plating catalyst having high adhesion to the substrate.
  • a polymer layer with low water absorption can be formed.
  • the plating film formed by applying a plating catalyst on this polymer layer and then performing a plating treatment has the effect of excellent adhesion to the polymer layer, and the polymer layer is difficult to retain moisture, ions, etc. Therefore, there are effects such as temperature and humidity dependence and no change in shape.
  • a resin substrate containing an epoxy resin, a polyimide resin, or a PET resin For the substrate on which the plating film is formed, it is preferable to use a resin substrate containing an epoxy resin, a polyimide resin, or a PET resin.
  • the nitrile group-containing polymerizable polymer of the present invention can be used as a composition by mixing with other components (for example, a solvent).
  • the content of the nitrile group-containing polymerizable polymer of the present invention should be in the range of 2% by mass to 50% by mass with respect to the total weight of the composition.
  • force S preferably in the range of 5% by mass to 30% by mass.
  • the solvent used in the composition containing the nitrile group-containing polymerizable polymer of the present invention is not particularly limited as long as the polymer can be dissolved. Further, a surfactant may be further added to the solvent.
  • Specific examples of the solvent that can be used are the same as the specific examples of the solvent that can be used in the composition of the compound having a polymerizable group and an interactive group (for example, a cyano group-containing polymerizable polymer). The specific example is also the same.
  • various conditions for example, the temperature of the composition, the concentration of each component, the conditions of additives, etc.
  • the composition containing the nitrile group-containing polymerizable polymer of the present invention is applied to coating applications are also included. The same conditions as those in the case of applying the composition containing the cyano group-containing polymerizable polymer.
  • a dimensionally stable plate-like material is preferably used as a base material used for forming a laminate using the composition containing the nitrile group-containing polymerizable polymer of the present invention. Any material can be used as long as it satisfies flexibility, strength, durability, etc., and is appropriately selected according to the purpose of use.
  • polyimide resin for example, polyimide resin, bismaleimide resin, polyphenylene oxide resin, epoxy resin, liquid crystal polymer, polytetrafluoroethylene resin, etc., silicone substrates, paper, and plastic are laminated.
  • Paper, metal plate for example, ano-remium, zinc, copper, etc.
  • the base material is insulative. It is preferable to use resin.
  • the base insulating film GX-13 (trade name, film thickness: 45 111) is heated and pressurized, and is bonded by a vacuum laminator at a pressure of 0.2 MPa under the conditions of 100 ° C to 110 ° C. Got.
  • an insulating composition containing a polymerization initiator having the following composition was applied onto the substrate by spin coating so as to have a thickness of 3 microns, and left at 30 ° C for 1 hour to remove the solvent. After removal, it was dried at 140 ° C. for 30 minutes to form a polymerization initiation layer (insulating polymerization initiation layer).
  • Bisphenol A type epoxy resin (epoxy equivalent: 185, manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 828) 20 parts by mass, cresol nopolac type epoxy resin (epoxy equivalent: 215, Dainippon Ink & Chemicals, Inc.) Product name: Epiclone N—673) 45 parts by mass, phenol nopolac resin (phenolic hydroxyl group equivalent 105, manufactured by Dainippon Ink & Chemicals, Inc., trade name: Phenolite) 30 parts by mass, ethyl diglycol acetate In 20 parts and 20 parts of sorbent naphtha, the mixture is heated and dissolved with stirring and cooled to room temperature.
  • Polymer A having a polymerizable group and an interactive group was synthesized as follows.
  • Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, power lens AOI (trade name, manufactured by Showa Denko KK) 18. 56 g, N, N-dimethylacetamide 19 g are added to the above reaction solution, The reaction was carried out at 55 ° C for 4 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane 1: 1, and the solid matter was taken out to obtain 32 g of polymer A having a polymerizable group and an interactive group (weight average molecular weight 150,000).
  • the prepared coating solution was applied onto the polymerization initiation layer of the substrate A1 by a spin coating method so as to have a thickness of 1 ⁇ m and dried at 80 ° C. for 30 minutes.
  • UV exposure machine (trade name: UVF- 502S, lamp: UXM- 501MD) using, 1. 5mW / cm 2 of irradiation path Wa (Ushio Denki manufactured accumulated UV actinometer (trade name: UIT150) and a light receiving sensor (quotient The product was irradiated for 660 seconds under the product name: UVD—S254) to produce a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1.
  • the integrated exposure was 990 mJ.
  • the substrate on which the graft polymer was formed was immersed in acetone in a stirred state for 5 minutes. It was pickled and subsequently washed with distilled water.
  • Substrate A2 having a polymer layer was immersed in a 1% acetone solution of palladium nitrate for 30 minutes, and then immersed in acetone for cleaning.
  • electroless plating was carried out at 60 ° C. for 5 minutes using the electroless plating bath having the following composition on the substrate A2 having a polymer layer provided with a plating catalyst.
  • the thickness of the obtained electroless copper plating film was 0.3 m.
  • an electrolytic copper plating bath having the following composition was used:
  • an etching resist is formed in a region to be left as a metal pattern (wiring pattern), and a plating film in a region having no resist is formed by etching with FeCl / HC1.
  • This comb-shaped wiring is allowed to stand for 200 hours under a HAST tester (trade name: AMI—150S-25, manufactured by ESPEC) at 125 ° C—85% relative humidity (unsaturated), applied voltage of 10 V, and 2 atm. As a result, no insulation failure was observed between the wires.
  • Example 11 Using the substrate A1 formed with the polymerization initiation layer prepared in Example 1, the following was performed. Thus, a surface metal film material was prepared.
  • Polymer B having a polymerizable group and an interactive group was synthesized as follows.
  • Ditertiary butyl hydroquinone 0.24 g, dibutyltin dilaurate 0.30 g, power lens AOI (trade name, manufactured by Showa Denko KK) 15.5 g, N, N-dimethylacetamide 16 g are added to the above reaction solution, The reaction was carried out at 55 ° C for 4 hours. Thereafter, 3. lg of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with distilled water, and the solid matter was taken out to obtain 30 g of polymer B having a polymerizable group and an interactive group (weight average molecular weight 17,000).
  • Polymer B having polymerizable group and interactive group B 7.9 parts by mass, 73.3 parts by mass of isopropanol, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide Then, a coating solution was prepared.
  • the prepared coating solution is applied by spin coating to a thickness of 1 ⁇ m on the polymerization initiation layer of the substrate A1 by spin coating, dried at 80 ° C. for 30 minutes, Using a UV exposure machine (product name: UVF-502S, lamp: UXM-501MD) manufactured by Electrical Electric Co., Ltd., with an irradiation power of 1.5 mW / cm 2 (ultraviolet integrated photometer (product name: UIT150) manufactured by Usio Electric Co., Ltd.) The photopolymer (trade name: measured by UVD—S254)) was irradiated for 660 seconds to form a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1.
  • the integrated exposure was 990 mj.
  • the substrate on which the graft polymer was produced was immersed in methanol in a stirred state for 5 minutes, and then washed with distilled water.
  • an etching resist is formed in a region to be left as a metal pattern (wiring pattern), and a plating film in a region having no resist is formed by etching with FeCl / HC1.
  • This comb-shaped wiring was allowed to stand for 200 hours at 125 ° C—85% relative humidity (unsaturated), an applied voltage of 10 V, and 2 atm using an ESPEC HAST tester (trade name: AMI—150S-25). However, the insulation failure between the wires was unseen.
  • substrate made of a polyimide film (trade name: Kapton 500H, manufactured by Toray DuPont) using a rod bar No. 18 and dried at 110 ° C for 10 minutes to undergo crosslinking reaction It was.
  • the film thickness of the obtained polymerization initiation layer was 9.3 111.
  • the substrate thus obtained was designated as substrate B1.
  • the surface roughness (Rz) of the obtained substrate B1 was 0.3 m.
  • Polymer A having Polymerizable Group and Interactive Group A 10.5 parts by mass, 7-3 parts by mass of methyl ethyl ketone ( ⁇ ), 33.9 parts by mass of methanol, and ⁇ , ⁇ dimethylacetamide 4.8 parts by mass Parts were mixed and stirred to prepare a coating solution.
  • the prepared coating solution was spin-coated on the polymerization initiation layer of the substrate B1 in the same manner as in Example 11 and then dried, followed by drying with a UV exposure machine (trade name: UVF-502S, lamp: UXM 501MD , using SanHisashi made Denki), 1. 5 mW / cm 2 of irradiation power (Ushio Denki made of ultraviolet integration actinometer (trade name: UIT150) and a light receiving sensor (trade name: UVD- S254) to more measurement)) Then, irradiation was performed for 800 seconds to form a graft polymer on the entire surface of the polymerization initiation layer of the substrate B1.
  • the integrated exposure was 1200 mJ.
  • the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, followed by washing with distilled water.
  • the 90 ° peel strength was 0 ⁇ 68kN / mm.
  • a substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen.
  • the base material was Kapton EN (trade name, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 m.
  • the saturated water absorption of this base material at 25 ° C.-50% relative humidity was 1.0% by mass.
  • An insulating resin composition having the following polymerization initiating ability is applied to both surfaces of this substrate (resin film) using the dipping method, dried at 100 ° C for 5 minutes, and then heated at 250 ° C for 30 minutes. Thus, a polymerization initiation layer (insulating polymerization initiation layer) was formed.
  • the saturated water absorption rate of the polymerization initiation layer at 25 ° C.-50% relative humidity was 1.2% by mass.
  • the obtained substrate was designated as substrate C1.
  • the surface roughness (Ra) of this substrate C1 was measured with Surfcom 3000A (trade name, manufactured by Tokyo Seimitsu Co., Ltd.) based on Ra of ISO 4288 (1996).
  • the obtained polyimide precursor was dissolved in N, N-dimethylacetamide (DMAc, manufactured by Wako Pure Chemical Industries, Ltd.) to give a 10% by mass solution.
  • DMAc N, N-dimethylacetamide
  • Polymer A having Polymerizable Group and Interactive Group A 10.5 parts by mass, 7-3 parts by mass of methyl ethyl ketone ( ⁇ ), 33.9 parts by mass of methanol, and 4.8 parts by mass of ⁇ , ⁇ -dimethylacetamide Were mixed and stirred to prepare a coating solution.
  • the prepared coating solution was applied on the polymerization initiation layers on both sides of the substrate C1 to a thickness of 1 m using the dipping method, dried at 80 ° C for 30 minutes, and then manufactured by Mitsunaga Electric.
  • UV exposure machine (trade name: UVF-502S, lamp: UXM-501MD) of 1.5mW / cm 2 irradiation power (Usio's UV integrated light meter (trade name: UIT150) and light receiving sensor (Trade name: measured by UVD-S254)) for 660 seconds to produce a graft polymer on the polymerization initiation layer of the substrate C1.
  • the integrated exposure was 990 mJ.
  • the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, followed by washing with distilled water.
  • the substrate C2 having the polymer layer was immersed in 1% acetone solution of palladium nitrate for 30 minutes and then immersed in acetone for cleaning.
  • the substrate C2 having a polymer layer provided with a plating catalyst was subjected to electroless plating at 60 ° C. for 5 minutes using the same electroless plating bath as in Example 11 above.
  • the thickness of the obtained electroless copper plating film on both sides was 0 ⁇ 3 m.
  • electroplating was performed for 20 minutes under the condition of 3 A / dm 2 using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the same composition as in Example 11 above.
  • the thicknesses of both sides of the obtained copper electroplating film were 18 m.
  • the obtained plated film was measured for a 90 ° peel strength at a tensile strength of 10 mm / min for a width of 5 mm in the same manner as in Example 11. The result was 0.668 kN / m.
  • Comb wiring (metal pattern) was formed on the substrate having the plating film obtained as described above using the same method as in Example 11.
  • Example 1 In 1 /, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was converted into a polymerizable group and an interactive group synthesized by the following method.
  • a polymer layer was formed in the same manner as in Example 1-1, except that the exposure condition was changed to irradiation with 100 mW / cm 2 irradiation power for 100 seconds instead of the polymer C having.
  • the integrated exposure was lOOOmJ.
  • a substrate A4 having a polymer layer was obtained.
  • the synthesized polymer C having a polymerizable group and an interactive group was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker).
  • the peak corresponding to the cyano group-containing unit is 4.3-4. 05 ppm (2H min) 2. 9-2. Broadly observed at 8ppm (2H min), 2 ⁇ 5—1.3ppm (3H min), and peaks corresponding to polymerizable group-containing units are 7 ⁇ 2-7.3ppm (lH min) , 6 ⁇ 4– 6 ⁇ 3 ppm (lH min), 6.2-6.
  • the 90 ° pinole strength was 0 ⁇ 75kN / mm.
  • Example 1 6 A substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen. [0316] Example 1 6
  • Example 1 In 1 /, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was converted into a polymerizable group and an interactive group synthesized by the following method.
  • a polymer layer was formed in the same manner as in Example 1-1, except that the exposure condition was changed to irradiation with 100 mW / cm 2 irradiation power for 100 seconds instead of the polymer D having.
  • the integrated exposure was lOOOmJ.
  • the synthesized polymer D having a polymerizable group and an interactive group was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). Peaks corresponding to nitrile group-containing units are broadly observed at 4.3-3.05 ppm (2H min), 2.9-1.8 ppm (2H min), 2.5-1.3 ppm (3H min) The peaks corresponding to the polymerizable group-containing units are 7 ⁇ 2–7.3 ppm (lH component), 6 ⁇ 4– 6 ⁇ 3 ppm (lH Min), 6.2-6.
  • a substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen.
  • Example 1 In 1! /, The polymerizable group and interaction used in forming the polymer layer The polymer A having a reactive group is replaced with the polymer E having a polymerizable group and an interactive group synthesized by the following method, and the exposure condition is irradiated for 100 seconds with an irradiation power of 10 mW / cm 2.
  • a polymer layer was formed in the same manner as in Example 1-1, except for changing to. Here, the integrated exposure was lOOOmJ.
  • NMR measurement was performed on the synthesized polymer E having a polymerizable group and an interactive group in the same manner as in Example 12.
  • the polymerizable group-containing unit: nitrile group-containing unit 23: 77 (mol ratio) It turns out that.
  • a substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen.
  • a metal pattern material was prepared as follows.
  • Example 1-1 a coating solution using Polymer A having a polymerizable group and an interactive group was prepared.
  • the prepared coating solution was applied by spin coating to a thickness of 1 ⁇ m on the polymerization initiation layer of the substrate A1 by spin coating, dried at 80 ° C. for 5 minutes, 10mW / using a UV exposure machine (product name: UVF-502S, lamp: UXM-501MD) manufactured by Electric Electric Irradiation was performed for 100 seconds with an irradiation power of cm 2 (measured with a UV integrated light meter (trade name: UIT150) and a light receiving sensor (trade name: UVD-S254) manufactured by Usio Denki).
  • a UV exposure machine product name: UVF-502S, lamp: UXM-501MD
  • Electric Electric Irradiation was performed for 100 seconds with an irradiation power of cm 2 (measured with a UV integrated light meter (trade name: UIT150) and a light receiving sensor (trade name: UVD-S254) manufactured by Usio Denki).
  • mask A or line 'and' space 100 ⁇ 111/100 ⁇ m with a pattern of 5 mm in width and 50 mm in length arranged at 0.1 mm intervals on substrate A1 coated with the coating solution and dried.
  • a mask B of mold wiring By placing and exposing a mask B of mold wiring, a graft polymer was formed in a pattern on the polymerization initiation layer of the substrate A1.
  • the integrated exposure was lOOOmJ.
  • the substrate on which the graft polymer was formed was immersed in agitated acetonitrile for 5 minutes, and then washed with distilled water.
  • substrates A7 (using mask A) and A8 (using mask B) having a pattern shape of 5 mm in width and 50 mm in length and having a polymer layer with a thickness of 0.5 m were obtained.
  • the substrate A7 having a polymer layer was immersed in a 0.1 wt% acetone solution of palladium nitrate for 30 minutes, and then immersed in acetone for cleaning.
  • the substrate A7 having a polymer layer provided with a plating catalyst was subjected to electroless plating at 60 ° C. for 15 minutes using an electroless plating bath having the following composition.
  • the thickness of the obtained electroless copper plating film was 0 ⁇ 50 m.
  • Example 1-1 using the electroless copper plating film as the power feeding layer, the same method as in Example 1-1 was used to form an electrolytic copper plating film with a thickness of 18 m on substrate A7 and a thickness of 10 ⁇ m on substrate A8. Electricity was turned on.
  • beta was performed at 100 ° C for 30 minutes and at 170 ° C for 1 hour.
  • the synthesized nitrile group-containing polymerizable polymer A is dissolved in heavy DMSO, and 300MHz N Measurement was performed with MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing unit 3-4. 05ppm (2H min), 2.9—2.8 ppm (2H min), 2.5—1.3 ppm (3H min) Peaks corresponding to polymerizable group-containing units are 7.2-7. 3 ppm (lH component), 6.4— 6. 3 ppm (lH component), 6.2 — 6.
  • An epoxy insulating film (product name: GX-1 3; Ajinomoto Fine-Techno Co., Ltd., film thickness: 45 m) is heated and pressurized on the glass epoxy substrate as an electrical insulating layer, and 0.2 MPa using a vacuum laminator.
  • the substrate A was obtained by bonding under conditions of 100 ° C. to 110 ° C.
  • an insulating composition containing a polymerization initiator having the following composition was applied onto substrate A by spin coating so as to have a thickness of 3 microns, and left at 30 ° C for 1 hour to remove the solvent. After the removal, it was dried at 140 ° C. for 30 minutes to form a polymerization initiation layer (insulating polymerization initiation layer).
  • Liquid bisphenol A type epoxy resin (epoxy equivalent 176, manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 825) 5g, MEK varnish of phenolic nopolak resin containing triazine structure (manufactured by Dainippon Ink & Chemicals, Inc., product) Name: Phenolite LA— 7052, Nonvolatile content: 62%, Non-volatile phenolic hydroxyl group equivalent: 120) 2 g, Phenoxy resin MEK ⁇ varnish (manufactured by Toto Kasei Co., Ltd., trade name: YP—50EK35, Non-volatile content: 35%) 10.7g, 2-hydroxy-4,1 (2-hydroxyethoxy) -2-methylpropiophenone 2.3g, MEK5.3g, 2-tuccinore 4-methinoreimidazo, 1nore as polymerization initiator 0.53 g was mixed and completely dissolved in WL to obtain an insulating composition containing a poly
  • the prepared coating solution was applied onto the polymerization initiation layer of the substrate A1 by a spin coating method so as to have a thickness of 1 ⁇ m and dried at 80 ° C. for 30 minutes.
  • UV exposure machine (trade name: UVF- 502S, lamp: UXM- 501MD) using, 1. 5mW / cm 2 of irradiation path Wa (Ushio Denki manufactured accumulated UV actinometer (trade name: UIT150) and a light receiving sensor (quotient Product name: Measured according to UVD—S254)))))))))))))))))))))))) for 660 seconds to react the nitrile group-containing polymerizable polymer A on the entire surface of the polymerization initiation layer of the substrate A1.
  • UV exposure machine (trade name: UVF- 502S, lamp: UXM- 501MD) using, 1. 5mW / cm 2 of irradiation path Wa (Ushio Denki manufactured accumulated UV actinometer
  • the substrate on which the photocured layer was formed was immersed in stirred acetone for 5 minutes, and then washed with distilled water.
  • Substrate A2 having a polymer layer was immersed in a 1% acetone solution of Pd for 30 minutes, and then immersed in acetone and washed.
  • electroless plating was carried out at 60 ° C. for 5 minutes using the electroless plating bath having the following composition on the substrate A2 having a polymer layer provided with a plating catalyst.
  • the thickness of the obtained electroless copper plating film was 0.3 m.
  • the pH of the plating bath having the above composition was adjusted to 12.5 (60 ° C) with sodium hydroxide and sulfuric acid.
  • electroplating was carried out for 20 minutes under the condition of 3 A / dm 2 using an electroless copper plating film with the electroless copper plating film as the power feeding layer. Thereafter, baking was performed at 120 ° C for 1 hour. The thickness of the obtained electrolytic copper plating film was 18 m.
  • an etching resist is formed in a region to be left as a metal pattern (wiring pattern), and a plating film in a region having no resist is formed by etching with FeCl / HC1.
  • This comb-shaped wire is connected to a £ 3? £ ⁇ 1-8 3-cutter (8 ⁇ [1 1503-25]), 125 ° C—85% relative humidity (unsaturated), applied voltage 10 V, 2 atm. Between left and left for 200 hours, between wiring No insulation failure was observed.
  • Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, power lens AOI (trade name, manufactured by Showa Denko KK) 18.56 g and N-methylpyrrolidone 19 g are added to the above reaction solution.
  • the reaction was performed at ° C for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water to take out a solid, and 25 g of the nitrile group-containing polymerizable polymer B of the present invention was obtained.
  • the synthesized nitrile group-containing polymerizable polymer B was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). Peaks corresponding to di-tolyl group-containing units are broadly observed at 4.3-3.05 ppm (2H min), 2.9—2.8ppm (2H min), 2.5-1-1.3 ppm (3H min) The peaks corresponding to the polymerizable group-containing units are 7.2-7.3 ppm (lH), 6.4—6.3 ppm (lH), 6.2—6.
  • a composition was prepared in the same manner as in Example 2-1, except that the nitrile group-containing polymerizable polymer B synthesized as described above was used, and this was used to form a laminate, which was then comb-shaped. Wiring (metal pattern material) was produced.
  • Example 2-2 In a 500 mL three-necked flask, add 1 mL of ethylene glycol diacetate, raise the temperature to 75 ° C, and add hydroxyethyl ateryl purified by the method described in Example 2-2 1. A mixed solution of 39 g, cyanoethyl attareione 6.00 g, V-601 (previously described): 0.1382 g, and 1 mL of ethylene glycol diacetate was added dropwise over 2.5 hours. After completion of dropping, the temperature was raised to 80 ° C. and reacted for 3 hours.
  • a composition was prepared in the same manner as in Example 2-1, except that the nitrile group-containing polymerizable polymer C synthesized as described above was used. Wiring (metal pattern material) was produced.
  • the synthesized nitrile group-containing polymerizable polymer D was subjected to NMR measurement in the same manner as in Example 2-2.
  • the polymerizable group-containing unit: nitrile group-containing unit 23: 77 (mol ratio). I understood.
  • Example 2-1 Except for using the nitrile group-containing polymerizable polymer D synthesized as described above, a composition was prepared in the same manner as in Example 2-1, and a laminate was formed using this. Comb wiring (metal pattern material) was prepared.
  • nitrile group-containing polymerizable polymers E to M of the present invention were synthesized in the following synthesis examples.
  • the synthesized nitrile group-containing polymerizable polymer E was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing units 3-4. 0 ppm (2H min), 2. 9— 2. 75 ppm (2 H min), 2.5— 1. 3 ppm (3 H min) Peaks corresponding to the polymerizable group-containing units are 7.4-7.
  • the synthesized nitrile group-containing polymerizable polymer F was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing unit 3-4. 05ppm (2H min), 2.9—2.8 ppm (2H min), 2.5—1.3 ppm (3H min) Peaks corresponding to polymerizable group-containing units are 7.2-7. 3 ppm (lH component), 6.4— 6. 3 ppm (lH component), 6.2 — 6. lppm (lH component), 6.0 — 5 • 9ppm (for 1H), 4 ⁇ 4-4. 05ppm (for 4H), 2 ⁇ 5–1. 3ppm (for 3H) The trityl group-containing unit is 23:77 (mol ratio).
  • the synthesized nitrile group-containing polymerizable polymer I was dissolved in heavy DMSO and measured with 300 MHz NM R (trade name: AV-300, manufactured by Bruker). Peak forces corresponding to nitrile group-containing units 25-4.
  • the synthesized nitrile group-containing polymerizable polymer J was dissolved in heavy DMSO and measured with 300 MHz NM R (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing units 2-3. 95 ppm (2H min), 2. 9— 2. 75 ppm (2 H min), 2.1 — 0.6 p pm (5 H min) , Peaks corresponding to polymerizable group-containing units are 7.4-7. Oppm (lH component), 6.1 — 6. Oppm (lH component), 5.7—5.6 ppm (lH component), 4.2 — 3 • 95ppm (6H min.), 3.
  • the synthesized nitrile group-containing polymerizable polymer K was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to a nitrile group-containing unit 9- 3.65 ppm (2H min), 2.5—2.3 ppm (2H min), 1.7—1.4 ppm (2H min), 1.4-1 lppm (4H min), 0.9—0.6 ppm (6H min), 2.5—1.3 3ppm (3H min) broadly observed, peaks corresponding to polymerizable group-containing units 7. Oppm (for 1H), 6. 4- 6. 3ppm (for 1H), 6.3— 6.
  • nitrile group-containing unit 25: The component force was 75 (mol ratio).
  • the synthesized nitrile group-containing polymerizable polymer L was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Acrylonitrile units are observed broadly at peak forces of 4.3-4.0ppm (2H min), 3.0-2.8ppm (2H min), and 2.7-1.4ppm (3H min) corresponding to Cyanethyl Atylate Ju A peak equivalent to 2.7-1.4 ppm (3H min) was observed broadly, and peak forces corresponding to polymerizable group-containing units S7.4—7.0 ppm (lH min), 6.4—6.3 ppm (lH min) , 6.3-6.

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Abstract

A process for producing a metallic-pattern-bearing material which comprises the steps of (a1) forming on a substrate a polymer layer made of a polymer which has a functional group interacting with a plating catalyst or a precursor therefor and is directly chemically bonded to the substrate, (a2) imparting the plating catalyst or precursor therefor to the polymer layer, (a3) plating the plating catalyst or precursor therefor, and (a4) pattern-wise etching the deposit film formed, wherein the polymer layer satisfies all of the following requirements (1) to (4). Requirement 1: to have a saturation water absorption as measured at 25°C and 50% of 0.01-10 mass%. Requirement 2: to have a saturation water absorption as measured at 25°C and 95% of 0.05-20 mass%. Requirement 3: to have a water absorption after 1-hour immersion in 100°C boiling water of 0.1-30 mass%. Requirement 4: to have a contact angle, as measured after dropping of 5 µL of distilled water thereonto and standing for 15 seconds, of 50-150 degrees at 25°C and 50%.

Description

明 細 書  Specification

表面金属膜材料とその作製方法、金属パターン材料とその作製方法、ポ リマー層形成用組成物、二トリル基含有ポリマーとその合成方法、二トリル基含有 ポリマーを用いた組成物、及び積層体  Surface metal film material and production method thereof, metal pattern material and production method thereof, polymer layer forming composition, nitrile group-containing polymer and synthesis method thereof, composition using nitrile group-containing polymer, and laminate

技術分野  Technical field

[0001] 本発明は、表面金属膜材料の作製方法、表面金属膜材料、金属パターン材料の 作製方法、金属パターン材料、及びポリマー層形成用組成物に関する。また本発明 は、二トリル基及び重合性基を含有する新規ポリマー、その合成方法、該ポリマーを 含有する組成物、及び該組成物を用いてなる積層体に関する。  The present invention relates to a method for producing a surface metal film material, a surface metal film material, a method for producing a metal pattern material, a metal pattern material, and a polymer layer forming composition. The present invention also relates to a novel polymer containing a nitrile group and a polymerizable group, a synthesis method thereof, a composition containing the polymer, and a laminate comprising the composition.

背景技術  Background art

[0002] 従来、絶縁性基板の表面に金属パターンによる配線を形成した金属配線基板が、 電子部品や半導体素子に広く用いられている。  Conventionally, a metal wiring board in which a wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.

力、かる金属パターン材料の作製方法としては、主に、「サブトラクティブ法」が使用さ れる。このサブトラクティブ法とは、基板表面に形成された金属膜上に、活性光線の 照射により感光する感光層を設け、この感光層を像様露光し、その後現像してレジス ト像を形成し、次いで、金属膜をエッチングして金属パターンを形成し、最後にレジス トを剥離する方法である。  The “subtractive method” is mainly used as a method for producing force and metal pattern materials. In this subtractive method, a photosensitive layer that is exposed to actinic rays is provided on a metal film formed on the surface of the substrate, this photosensitive layer is exposed imagewise, and then developed to form a resist image. Next, the metal film is etched to form a metal pattern, and finally the resist is peeled off.

[0003] この方法により得られる金属パターンにおいては、基板表面に凹凸を設けることに より生じるアンカー効果により、基板と金属膜との間の密着性を発現させている。その ため、得られた金属パターンの基板界面部の凹凸に起因して、金属配線として使用 する際の高周波特性が悪くなるという問題点があった。また、基板表面に凹凸化処理 するためには、クロム酸などの強酸で基板表面を処理するが必要であるため、金属 膜と基板との密着性に優れた金属パターンを得るためには、煩雑な工程が必要であ るという問題点があった。  [0003] In the metal pattern obtained by this method, adhesion between the substrate and the metal film is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, there is a problem that the high frequency characteristics when used as a metal wiring deteriorate due to the unevenness of the obtained metal pattern at the interface of the substrate. Also, in order to obtain a metal pattern with excellent adhesion between the metal film and the substrate, it is necessary to treat the substrate surface with a strong acid such as chromic acid in order to make the surface of the substrate uneven. There is a problem that a complicated process is necessary.

[0004] この問題を解決するため、基板の表面にプラズマ処理を行い、基板表面に重合開 始基を導入し、その重合開始基からモノマーを重合させて、基板表面に極性基を有 する表面グラフトポリマーを生成させるという表面処理を行うことで、基板の表面を粗 面化することなぐ基板と金属膜との密着性を改良させる方法が提案されている（例え ば、非特許文献 1参照）。し力もながら、この方法によれば、グラフトポリマーが極性基 を有することから、温度や湿度変化により水分の吸収や脱離が生じ易ぐその結果、 形成された金属膜や基板が変形してしまうとレ、う問題を有して!/、た。 [0004] In order to solve this problem, plasma treatment is performed on the surface of the substrate, a polymerization initiating group is introduced on the surface of the substrate, a monomer is polymerized from the polymerization initiating group, and a surface having a polar group on the substrate surface The surface of the substrate is roughened by a surface treatment that produces a graft polymer. There has been proposed a method for improving the adhesion between the substrate and the metal film without facing (for example, see Non-Patent Document 1). However, according to this method, since the graft polymer has a polar group, moisture absorption and desorption easily occur due to changes in temperature and humidity, and as a result, the formed metal film and substrate are deformed. I have a problem!

また、この方法を利用して得られた金属パターンを金属配線基板の配線として使用 する際には、基板界面部分に極性基を有するグラフトポリマーが残存し、水分ゃィォ ン等を保持しやすくなるため、温'湿度依存性や配線間の耐イオンマイグレーション 性や、形状の変化に懸念があった。特に、プリント配線板などの微細配線に適用した 際には、配線 (金属パターン）間における高い絶縁性が必要であり、配線間の絶縁信 頼性のより一層の向上が要求されているのが現状である。  In addition, when the metal pattern obtained by using this method is used as the wiring of a metal wiring board, a graft polymer having a polar group remains at the interface portion of the board, so that moisture ions and the like are easily retained. Therefore, there were concerns about temperature and humidity dependence, resistance to ion migration between wires, and changes in shape. In particular, when applied to fine wiring such as printed wiring boards, high insulation between wirings (metal patterns) is required, and further improvement in insulation reliability between wirings is required. Currently.

[0005] 光硬化性樹脂組成物は、その優れた特徴から、上記のような表面処理用途の材料 としてのみならず、レジスト材料、印刷版用材料、コーティング材料、光造形用材料な どにも使用されてレ、る。光硬化性樹脂組成物の中でもラジカル重合で硬化する材料 としては、一般的に、バインダー、多官能モノマー、光重合開始剤から構成される。こ の際に、光硬化感度を向上させる手法として、重合性基を有するバインダーを用いる 方法がある。 [0005] Due to its excellent characteristics, the photocurable resin composition is not only used as a material for surface treatment as described above, but also as a resist material, a printing plate material, a coating material, an optical modeling material, and the like. Used. Among the photocurable resin compositions, the material that is cured by radical polymerization is generally composed of a binder, a polyfunctional monomer, and a photopolymerization initiator. In this case, as a method for improving the photocuring sensitivity, there is a method using a binder having a polymerizable group.

[0006] 一方、表面処理材料、特に、めっき膜を形成するための表面処理材料は、めっき触 媒を吸着させる機能が必要となる。一般的に、めっき触媒に対する吸着性基としては 、カルボン酸基、水酸基、エーテル基などが知られているが、これらの官能基は親水 性が高ぐ水分やイオン等を保持しやすくなるため、形成されためつき膜の温 ·湿度 依存性や、形状の変化に影響を与えるといった懸念があった。  [0006] On the other hand, a surface treatment material, particularly a surface treatment material for forming a plating film, needs a function of adsorbing a plating catalyst. Generally, carboxylic acid groups, hydroxyl groups, ether groups, and the like are known as adsorptive groups for the plating catalyst, but these functional groups are highly hydrophilic and easily retain moisture, ions, etc. There was concern that the formed film would depend on the temperature / humidity of the attached film and would affect the shape change.

この懸念に対し、めっき触媒に対する吸着性と疎水性を両立する官能基としてシァ ノ基 (二トリル基）を用いる方法が考えられて!/、る。  In response to this concern, a method using a cyano group (nitrile group) as a functional group that achieves both adsorption to the plating catalyst and hydrophobicity is conceivable!

[0007] そのようなシァノ基と重合性基とを有するポリマーとしては、以下のモノマーを用い てァニオン重合で合成されたものが知られている（例えば、特許文献 1参照）。  As such a polymer having a cyano group and a polymerizable group, a polymer synthesized by anion polymerization using the following monomers is known (for example, see Patent Document 1).

CH =C (CN) COOR1OOCCH = CH (R1は低級アルキレン基） CH = C (CN) COOR 1 OOCCH = CH (R 1 is a lower alkylene group)

2 2  twenty two

この合成方法では、ァニオン重合が微量の水分で進行してしまい、ハンドリングが 難しいという問題点がある。 [0008] また、例えば、特許文献 2には、以下のマクロモノマーの記載がある c This synthesis method has a problem that the anion polymerization proceeds with a very small amount of water and is difficult to handle. [0008] Further, for example, Patent Document 2 describes the following macromonomer c

[0009] [化 1] [0009] [Chemical 1]

Figure imgf000004_0001
Figure imgf000004_0001

[0010] しかし、上記マクロモノマーではポリマー中の重合性基が少なぐ硬化性（重合性） が低いこと、また、ポリマー分子内のシァノ基の含率も低いため、めっき触媒に対する 吸着性に懸念があった。 [0010] However, the macromonomer described above has a low curability (polymerizability) with a small amount of polymerizable groups in the polymer, and also has a low content of cyan groups in the polymer molecule. was there.

特許文献 1 :特開平 11 106372号公報  Patent Document 1: JP-A-11 106372

特許文献 2：特開 2004— 176025号公報  Patent Document 2: Japanese Patent Application Laid-Open No. 2004-176025

非特許文献 1 : Advanced Materials 2000年 20号 1481— 1494  Non-Patent Document 1: Advanced Materials 2000 No. 20 1481— 1494

発明の開示  Disclosure of the invention

発明が解決しょうとする課題  Problems to be solved by the invention

[0011] 本発明は、上記従来の技術の欠点を考慮してなされたものである。 [0011] The present invention has been made in consideration of the above-mentioned drawbacks of the conventional techniques.

即ち、本発明は、金属膜の密着性に優れ、湿度変化による密着力の変動が少ない 表面金属膜材料、及びその作製方法を提供する。  That is, the present invention provides a surface metal film material that is excellent in adhesion of a metal film and has little fluctuation in adhesion due to changes in humidity, and a method for producing the same.

また、本発明は、金属パターンの非形成領域の絶縁信頼性に優れた金属パターン 材料、及びその作製方法を提供する。  In addition, the present invention provides a metal pattern material excellent in insulation reliability in a region where a metal pattern is not formed, and a method for manufacturing the same.

更に、本発明は、吸水性が低ぐ疎水性が高ぐ更に、めっき触媒又はその前駆体 に対する吸着性に優れたポリマー層を形成し得るポリマー層形成用組成物を提供す 更に、本発明は、めっき触媒等の金属に対して十分な吸着性を有し、更に、重合性 にも優れた新規ポリマー、それを用いた組成物、及び積層体を提供する。  Furthermore, the present invention provides a composition for forming a polymer layer that can form a polymer layer that has low water absorption and high hydrophobicity, and that is excellent in adsorption to the plating catalyst or its precursor. The present invention provides a novel polymer having sufficient adsorptivity to a metal such as a plating catalyst and excellent in polymerizability, a composition using the same, and a laminate.

課題を解決するための手段  Means for solving the problem

[0012] 本発明は、第 1の表面金属膜材料の作製方法として、（al)基板上に、めっき触媒 又はその前駆体と相互作用を形成する官能基を有し、且つ、該基板と直接化学結合 したポリマーからなるポリマー層を形成する工程と、（a2)該ポリマー層にめっき触媒 又はその前駆体を付与する工程と、 (a3)該めっき触媒又はその前駆体に対してめつ きを行う工程と、を有し、前記ポリマー層が下記 1〜4の条件の全てを満たすことを特 徴とする、当該方法を提供する。 [0012] The present invention provides a method for producing a first surface metal film material comprising: (al) a functional group that forms an interaction with a plating catalyst or a precursor thereof on a substrate; Chemical bond A step of forming a polymer layer comprising the polymer obtained, (a2) a step of applying a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of performing a test on the plating catalyst or the precursor thereof. And the polymer layer satisfies all of the following conditions 1 to 4.

条件 1 : 25°C— 50%相対湿度環境下における飽和吸水率が 0. 01〜； 10質量％ 条件 2 : 25°C— 95%相対湿度環境下における飽和吸水率が 0. 05〜20質量％ 条件 3 : 100°C煮沸水に 1時間浸漬した後の吸水率が 0. ；!〜 30質量％  Condition 1: 25 ° C—Saturated water absorption in a 50% relative humidity environment is 0.01 to 10 mass% Condition 2: 25 ° C—Saturated water absorption in a 95% relative humidity environment is 0.05 to 20 mass % Condition 3: Water absorption after immersion in boiling water at 100 ° C for 1 hour is 0;

条件 4 : 25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置 後の表面接触角が 50〜 150度  Condition 4: 25 ° C — In a 50% relative humidity environment, 5 ^ L of distilled water is dropped and the surface contact angle after standing for 15 seconds is 50 to 150 degrees.

[0013] 本発明において、前記ポリマー層が下記;！'〜 4 'の条件の全てを満たすことが好ま しい。 [0013] In the present invention, the polymer layer is: It is preferable to satisfy all the conditions of '~ 4'.

条件 1 ' : 25°C— 50%相対湿度環境下における飽和吸水率が 0. 0；!〜 5質量％ 条件 2' : 25°C— 95%相対湿度環境下における飽和吸水率が 0. 05〜； 10質量％ 条件 3' : 100°C煮沸水に 1時間浸漬した後の飽和吸水率が 0. ；!〜 20質量％ 条件 4' : 25°C— 50%相対湿度環境下において、蒸留水 5 しを滴下し、 15秒静 置後の表面接触角が 55〜150度  Condition 1 ': 25 ° C—Saturated water absorption at 50% relative humidity is 0.0; 0 to 5% by mass Condition 2': 25 ° C—Saturated water absorption at 95% relative humidity is 0.05 ~; 10% by mass Condition 3 ': Saturated water absorption after immersion in boiling water at 100 ° C for 1 hour is 0.;! ~ 20% by mass Condition 4': 25 ° C-distilled at 50% relative humidity The surface contact angle after dropping for 5 seconds and standing for 15 seconds is 55 to 150 degrees.

[0014] 更に、本発明における（al)工程は、基板上に、めっき触媒又はその前駆体と相互 作用を形成する官能基、及び重合性基を有するポリマーを直接化学結合させること により行われることが好まし!/、。 [0014] Furthermore, the step (al) in the present invention is performed by directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor on the substrate. Is preferred!

また、（al)工程が、（al— 1)基材上に、重合開始剤を含有する、又は重合開始可 能な官能基を有する重合開始層が形成された基板を作製する工程と、（al— 2)該重 合開始層に、めっき触媒又はその前駆体と相互作用を形成する官能基、及び重合 性基を有するポリマーを直接化学結合させると、を含むことも好ましレ、態様である。  In addition, the (al) step includes (al-1) a step of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; al-2) It is also preferable that the polymerization initiating layer includes a chemical group directly having a functional group that interacts with the plating catalyst or its precursor and a polymer having a polymerizable group. is there.

[0015] 本発明において、前記めつき触媒又はその前駆体と相互作用を形成する官能基、 及び重合性基を有するポリマーが、下記式（1)で表されるユニット、及び、下記式（2) で表されるユニットを含む共重合体であることが好ましい。 [0015] In the present invention, a polymer having a functional group that interacts with the plating catalyst or a precursor thereof, and a polymerizable group includes a unit represented by the following formula (1), and the following formula (2 It is preferable that it is a copolymer containing the unit represented by this.

[0016] [化 2] [0016] [Chemical 2]

Figure imgf000006_0001
Figure imgf000006_0001

[0017] 上記式（1)及び式（2)中、！^〜 は、各々独立に、水素原子、又は置換もしくは無 置換のアルキル基を表し、 X、 Y及び Zは、各々独立に、単結合、又は置換もしくは無 置換の二価の有機基、エステル基、アミド基、又はエーテル基を表し、 L1及び L2は、 各々独立に、置換もしくは無置換の二価の有機基を表す。 [0017] In the above formula (1) and formula (2),! ^ ~ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group or ester group. Represents an amide group or an ether group, and L 1 and L 2 each independently represents a substituted or unsubstituted divalent organic group.

[0018] また、本発明において、前記めつき触媒又はその前駆体と相互作用を形成する官 能基、及び重合性基を有するポリマーの重量平均分子量が 20000以上であることが 好ましい態様である。  [0018] Further, in the present invention, it is a preferred embodiment that the weight average molecular weight of the polymer having a functional group that forms an interaction with the metal catalyst or its precursor and a polymerizable group is 20000 or more.

[0019] 本発明の第 2の表面金属膜材料の作製方法は、（al ' )基板上に、シァノ基を有し、 且つ、該基板と直接化学結合したポリマーからなるポリマー層を形成する工程と、 (a 2)該ポリマー層にめっき触媒又はその前駆体を付与する工程と、（a3)該めっき触媒 又はその前駆体に対してめつきを行う工程と、を有することを特徴とする。  [0019] The second surface metal film material production method of the present invention includes a step of forming a polymer layer made of a polymer having a cyano group and directly bonded to the substrate on an (al ') substrate. And (a2) a step of imparting a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of performing contact with the plating catalyst or the precursor thereof.

また、（al ' )工程は、基板上に、シァノ基及び重合性基を有するポリマーを直接化 学結合させることにより行われるが好ましい態様である。  In addition, the (al ′) step is preferably performed by directly chemically bonding a polymer having a cyano group and a polymerizable group on a substrate.

更に、（al ' )工程が、（al— 1 ' )基材上に、重合開始剤を含有する、又は重合開始 可能な官能基を有する重合開始層が形成された基板を作製する工程と、 (al - 2 ' ) 該重合開始層に、シァノ基及び重合性基を有するポリマーを直接化学結合させると 、を含むことも好ましい態様である。 加えて、前記シァノ基及び重合性基を有するポリマーの重量平均分子量が 20000 以上であることが好ましレ、態様である。 Further, the (al ′) step is a step of producing a substrate in which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a (al-1 ′) base material; It is also a preferred embodiment that (al-2 ′) contains a polymer having a cyano group and a polymerizable group directly chemically bonded to the polymerization initiation layer. In addition, the weight average molecular weight of the polymer having a cyano group and a polymerizable group is preferably 20000 or more.

[0020] 本発明において、（a3)工程では、無電解めつきが行われることが好ましぐ該無電 解めつきの後に、更に電気めつきが行われることがより好ましい。 [0020] In the present invention, in the step (a3), it is preferable that electroless plating is performed. It is more preferable that electrical plating is further performed after the electroless plating.

また、本発明における（a2)工程で用いられるめっき触媒はパラジウムであることが 好ましい。  In addition, the plating catalyst used in the step (a2) in the present invention is preferably palladium.

[0021] 本発明の第 3の表面金属膜材料の作製方法は、（al")樹脂フィルムの両面に対し て、めっき触媒又はその前駆体と相互作用を形成する官能基を有し、且つ、該基板 と直接化学結合したポリマーからなるポリマー層を形成する工程と、（a2)該ポリマー 層にめっき触媒又はその前駆体を付与する工程と、（a3)該めっき触媒又はその前 駆体に対してめつきを行う工程と、を有し、前記ポリマー層が下記;!〜 4の条件の全て を満たすことを特徴とする。  [0021] The third surface metal film material production method of the present invention comprises (al ") a functional group that interacts with the plating catalyst or its precursor on both sides of the resin film, and A step of forming a polymer layer comprising a polymer directly chemically bonded to the substrate; (a2) a step of applying a plating catalyst or a precursor thereof to the polymer layer; and (a3) the plating catalyst or a precursor thereof. And a step of performing tapping, wherein the polymer layer satisfies all of the following conditions;

条件 1 : 25°C— 50%相対湿度環境下における飽和吸水率が 0. 01〜； 10質量％ 条件 2 : 25°C— 95%相対湿度環境下における飽和吸水率が 0. 05〜20質量％ 条件 3 : 100°C煮沸水に 1時間浸漬した後の吸水率が 0. ；!〜 30質量％ 条件 4 : 25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置 後の表面接触角が 50〜 150度  Condition 1: 25 ° C—Saturated water absorption in a 50% relative humidity environment is 0.01 to 10 mass% Condition 2: 25 ° C—Saturated water absorption in a 95% relative humidity environment is 0.05 to 20 mass % Condition 3: The water absorption after immersion in boiling water at 100 ° C for 1 hour is 0.;! ~ 30% by mass Condition 4: 25 ° C—50% relative humidity is added dropwise with 5 ^ L of distilled water. Surface contact angle after standing for 15 seconds is 50 to 150 degrees

つまり、本発明の第 3の表面金属膜材料の作製方法によれば、（al")工程により、 基板として樹脂フィルムを用い、その両面にポリマー層を形成し、更に、（a2)工程、 及び (a3)工程を行うことで、両面に金属膜が形成された表面金属膜材料を得ること ができる。  That is, according to the third method for producing a metal film material for a surface of the present invention, a resin film is used as a substrate and a polymer layer is formed on both sides by the (al ") step. By performing the step (a3), a surface metal film material having a metal film formed on both surfaces can be obtained.

なお、前記（al ")工程、前記（a2)工程、及び前記（a3)工程は、各工程毎に、前記 樹脂フィルムの両面に対して同時に行われることが好ましい。  The step (al "), the step (a2), and the step (a3) are preferably performed simultaneously on both sides of the resin film for each step.

[0022] 本発明の表面金属膜材料は、本発明の表面金属膜材料の作製方法により得られ たものである。 [0022] The surface metal film material of the present invention is obtained by the method for producing a surface metal film material of the present invention.

[0023] また、本発明の第 1のポリマー層形成用組成物は、シァノ基及び重合性基を有する ポリマーと、該ポリマーを溶解しうる溶剤と、を含有し、本発明の表面金属膜材料の作 製方法に用いられることを特徴とする。 本発明の第 2のポリマー層形成用組成物は、 O （CH ) O （nは;!〜 5の整 [0023] The first polymer layer forming composition of the present invention contains a polymer having a cyano group and a polymerizable group, and a solvent capable of dissolving the polymer, and the surface metal film material of the present invention. It is used for the production method of The second polymer layer-forming composition of the present invention comprises O (CH) O (n is;

2 n  2 n

数)で表される構造、及び重合性基を有するポリマーと、該ポリマーを溶解しうる溶剤 と、を含有し、本発明の表面金属膜材料の作製方法に用いられることを特徴とする。  And a polymer having a polymerizable group and a solvent capable of dissolving the polymer, and is used in the method for producing a surface metal film material of the present invention.

[0024] 本発明の金属パターン材料の作製方法は、（a4)本発明の表面金属膜材料の作製 方法により得られた表面金属膜材料のめっき膜をパターン状にエッチングする工程 を有することを特徴とする。  [0024] The method for producing a metal pattern material of the present invention comprises (a4) a step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material of the present invention into a pattern. And

つまり、金属パターン材料の作製方法は、前述の表面金属膜材料の作製方法にお ける（al)、 （a2)、 （a3)工程を行った後、形成されためつき膜をパターン状にエツチン グする工程〔（a4)工程〕を行うものである。  In other words, the metal pattern material is produced by performing the steps (al), (a2), and (a3) in the above-described surface metal film material production method, and then etching the masked film into a pattern. Step [Step (a4)] is performed.

[0025] また、本発明の金属パターン材料は、本発明の金属パターン材料の作製方法によ り得られたものである。 [0025] The metal pattern material of the present invention is obtained by the method for producing a metal pattern material of the present invention.

[0026] また、本発明は、下記式（1)で表されるユニット、及び、下記式（2)で表されるュニッ トを含むことを特徴とするポリマーを提供する。  [0026] The present invention also provides a polymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2).

[0027] [化 3] [0027] [Chemical 3]

Figure imgf000008_0001
式 （ 1 ) 式 ( 2 )
Figure imgf000008_0001
Equation (1) Equation (2)

式（1)及び式（2)中、！^〜 は、各々独立に、水素原子、又は置換もしくは無置換 のアルキル基を表し、 X、 Y及び Zは、各々独立に、単結合、置換もしくは無置換の二 価の有機基、エステル基、アミド基、又はエーテル基を表し、 L1及び L2は、各々独立 に、置換もしくは無置換の二価の有機基を表す。 In formula (1) and formula (2),! ^ ~ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y and Z each independently represent a single bond, a substituted or unsubstituted divalent organic group, an ester group, Represents an amide group or an ether group, and L 1 and L 2 are each independently Represents a substituted or unsubstituted divalent organic group.

[0029] 本発明のポリマーにおいて、前記式（1)で表されるユニットが、下記式（3)で表され るユニットであることが好ましレ、。 [0029] In the polymer of the present invention, the unit represented by the formula (1) is preferably a unit represented by the following formula (3).

[0030] [化 4]  [0030] [Chemical 4]

Figure imgf000009_0001
Figure imgf000009_0001

式 ( 3 )  Formula (3)

[0031] 式（3)中、 R1及び R2は、各々独立に、水素原子、又は置換もしくは無置換のアルキ ル基を表し、 Zは、単結合、置換もしくは無置換の二価の有機基、エステル基、アミド 基、又はエーテル基を表し、 Wは、酸素原子、又は NR(Rは、水素原子、又はアルキ ル基を表す。）を表し、 L1は、置換もしくは無置換の二価の有機基を表す。 In the formula (3), R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond, a substituted or unsubstituted divalent organic group. Group represents an ester group, an amide group, or an ether group, W represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group), and L 1 represents a substituted or unsubstituted divalent group. Represents a valent organic group.

[0032] 更に、本発明のポリマーとしては、前記式（3)で表されるユニットが、下記式 (4)で 表されるユニットであることが好ましレ、。  [0032] Further, as the polymer of the present invention, it is preferable that the unit represented by the formula (3) is a unit represented by the following formula (4).

[0033] [化 5] [0033] [Chemical 5]

Figure imgf000010_0001
式 （4 )
Figure imgf000010_0001
Formula (4)

[0034] 式 (4)中、 R1及び R2は、各々独立に、水素原子、又は置換もしくは無置換のアルキ ル基を表し、 V及び Wは、各々独立に、酸素原子、又は NR(Rは、水素原子、又はァ ルキル基を表す。）を表し、 L1は、置換もしくは無置換の二価の有機基を表す。 In formula (4), R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent an oxygen atom or NR ( R represents a hydrogen atom or an alkyl group.) L 1 represents a substituted or unsubstituted divalent organic group.

[0035] 前記式 (4)における Wが酸素原子であることが好ましい態様である。  [0035] In the above formula (4), W is preferably an oxygen atom.

また、前記式（1)、式（3)、又は式 (4)における L1がウレタン結合又はウレァ結合を 有する二価の有機基であることが好ましレ、。 In addition, it is preferable that L 1 in the formula (1), formula (3), or formula (4) is a divalent organic group having a urethane bond or a urea bond.

更に、前記式（1)、式（3)、又は式 (4)における L1が総炭素数 1〜9である二価の有 機基であることがより好ましレ、。 Furthermore, it is more preferable that L 1 in the formula (1), formula (3), or formula (4) is a divalent organic group having 1 to 9 total carbon atoms.

[0036] 本発明のポリマーにおいて、前記式（2)で表されるユニットが、下記式（5)で表され るユニットであることが好ましレ、。  [0036] In the polymer of the present invention, the unit represented by the formula (2) is preferably a unit represented by the following formula (5).

[0037] [化 6] [0037] [Chemical 6]

Figure imgf000011_0001
式 ( 5 )
Figure imgf000011_0001
Formula (5)

[0038] 式（5)中、 R5は、水素原子、又は置換もしくは無置換のアルキル基を表し、 Uは、酸 素原子、又は NR' (R'は、水素原子、又はアルキル基を表す。）を表し、 L2は、置換 もしくは無置換の二価の有機基を表す。 In formula (5), R 5 represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents an oxygen atom, or NR ′ (R ′ represents a hydrogen atom or an alkyl group) L 2 represents a substituted or unsubstituted divalent organic group.

[0039] 前記式（5)における L2中のシァノ基との連結部位力 直鎖、分岐、又は環状のアル キレン基を有する二価の有機基であることが好ましぐ該シァノ基との連結部位に、直 鎖、分岐、又は環状のアルキレン基を有する二価の有機基が、総炭素数;!〜 10であ ることがより好ましい。 [0039] Connection site strength with the cyan group in L 2 in the above formula (5) is preferably a divalent organic group having a linear, branched, or cyclic alkylene group. More preferably, the divalent organic group having a linear, branched, or cyclic alkylene group at the linking site has a total carbon number;

また、前記式（5)における L5中のシァノ基との連結部位力 芳香族基を有する二価 の有機基であることが好ましぐ該シァノ基との連結部位に、芳香族基を有する二価 の有機基が、総炭素数 6〜； 15であることがより好ましい。 Moreover, it is preferable that it is a divalent organic group having an aromatic group, which has an aromatic group at the site connected to the cyano group in L 5 in the formula (5). More preferably, the divalent organic group has a total carbon number of 6 to 15;

[0040] 本発明の新規ポリマーにおいて、前記式（1)、式（3)、又は式 (4)における L1がゥ レタン結合を有する二価の有機基であることが好ましい態様である。 [0040] In the novel polymer of the present invention, L 1 in the formula (1), formula (3), or formula (4) is preferably a divalent organic group having a urethane bond.

また、この新規ポリマーは、重量平均分子量が 2万以上であることが好ましい。  The novel polymer preferably has a weight average molecular weight of 20,000 or more.

[0041] 本発明の新規ポリマーにおいて、前記式（1)、式（3)、又は式 (4)における L1がゥ レタン結合を有する二価の有機基であるポリマーの合成方法（本発明のポリマーの合 成方法）について説明する。 [0041] In the novel polymer of the present invention, a method for synthesizing a polymer in which L 1 in the formula (1), formula (3), or formula (4) is a divalent organic group having a urethane bond (in the present invention, The polymer synthesis method) will be described.

本発明のポリマーの合成方法は、少なくとも溶媒中で、側鎖にヒドロキシル基を有 するポリマー、及び、イソシァネート基と重合性基とを有する化合物を用い、該ヒドロ キシル基に該イソシァネート基を付加させることにより L1中のウレタン結合を形成する ことを特徴とする。 The polymer synthesis method of the present invention uses a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group at least in a solvent. A urethane bond in L 1 is formed by adding the isocyanate group to a xyl group.

[0042] 本発明のポリマーの合成方法では、側鎖にヒドロキシル基を有するポリマーが、下 記（1)〜（4)の工程を順次経ることで得られたヒドロキシル基含有 (メタ）アタリレートを 用いて合成されたものであることが好ましレ、。  [0042] In the polymer synthesis method of the present invention, a hydroxyl group-containing (meth) acrylate obtained by sequentially polymerizing a polymer having a hydroxyl group in the side chain through the following steps (1) to (4): It is preferred that it is synthesized using.

(1)ヒドロキシノレ基含有 (メタ）アタリレートと、該ヒドロキシノレ基含有 (メタ）アタリレートを 合成する際に副生する 2官能アタリレートと、を含む混合物を、水に溶解する工程 (1) A step of dissolving, in water, a mixture containing a hydroxyl group-containing (meth) acrylate and a bifunctional acrylate which is by-produced when synthesizing the hydroxyl group-containing (meth) acrylate.

(2)得られた水溶液に、水と分離する第 1の有機溶剤を加えた後、該第 1の有機溶剤 と前記 2官能アタリレートとを含む層を水層から分離する工程 (2) A step of adding a first organic solvent that separates from water to the obtained aqueous solution, and then separating a layer containing the first organic solvent and the bifunctional acrylate from the aqueous layer.

(3)前記水層に、前記ヒドロキシル基含有 (メタ）アタリレートよりも水溶解性の高!/、化 合物を溶解する工程  (3) A step of dissolving a compound having a higher water solubility than the hydroxyl group-containing (meth) acrylate in the aqueous layer.

(4)前記水層に第 2の有機溶剤を加えて、前記ヒドロキシル基含有 (メタ）アタリレート を抽出した後、濃縮する工程  (4) A step of adding a second organic solvent to the aqueous layer, extracting the hydroxyl group-containing (meth) acrylate, and then concentrating it.

[0043] 更に、前記（1)〜（4)の工程を順次経ることで得られたヒドロキシル基含有 (メタ）ァ タリレートを含む単離物力 その全質量中に前記 2官能アタリレートを 0質量％以上 0 [0043] Furthermore, the isolation force containing the hydroxyl group-containing (meth) acrylate obtained through the steps (1) to (4) in succession, 0 mass% of the bifunctional acrylate in the total mass. 0 or more

. 10質量％以下の範囲で含むことが好ましい態様である。 It is a preferred embodiment that it is contained in the range of 10% by mass or less.

[0044] また、本発明のポリマーの合成方法において、用いられる溶媒は、 SP値 (沖津法に より算出）が 20〜23MPa1/2であることが好ましぐエステル系溶媒であることがより好 ましぐジアセテート系溶媒であることが更に好ましい。 [0044] Further, in the polymer synthesis method of the present invention, the solvent used is preferably an ester solvent having an SP value (calculated by the Okitsu method) of 20 to 23 MPa 1/2. More preferred is a diacetate solvent.

[0045] 本発明の組成物は、本発明のポリマーと、ケトン系溶剤又は二トリル系溶剤と、を含 有することを特徴とし、特に、その組成物中のポリマーの濃度力 2質量％〜50質量[0045] The composition of the present invention is characterized by containing the polymer of the present invention and a ketone solvent or a nitrile solvent, and in particular, the concentration force of the polymer in the composition is 2 mass% to 50 mass%. mass

%であることが好ましい。 % Is preferred.

また、本発明の積層体は、本発明の組成物を樹脂基材上に塗布してなることを特 徴とする。  The laminate of the present invention is characterized in that the composition of the present invention is applied on a resin substrate.

発明の効果  The invention's effect

[0046] 本発明によれば、金属膜の密着性に優れ、湿度変化による密着力の変動が少ない 表面金属膜材料、及びその作製方法を提供することができる。  According to the present invention, it is possible to provide a surface metal film material that is excellent in adhesion of a metal film and has little fluctuation in adhesion due to humidity change, and a method for manufacturing the same.

また、本発明によれば、金属パターンの非形成領域の絶縁信頼性に優れた金属パ ターン材料、及びその作製方法を提供することができる。 In addition, according to the present invention, the metal pattern having excellent insulation reliability in the non-formation region of the metal pattern. A turn material and a manufacturing method thereof can be provided.

また、本発明によれば、吸水性が低ぐ疎水性が高ぐ更に、めっき触媒又はその 前駆体に対する吸着性に優れたポリマー層を形成し得るポリマー層形成用組成物を 提供すること力でさる。  In addition, according to the present invention, it is possible to provide a composition for forming a polymer layer that can form a polymer layer that has a low water absorption and a high hydrophobicity, and further has an excellent adsorptivity to the plating catalyst or its precursor. Monkey.

更に、本発明によれば、めっき触媒等の金属に対して十分な吸着性を有し、更に、 重合性にも優れた新規ポリマー、その合成方法、該新規ポリマーを用いた組成物、 及び積層体を提供することができる。  Furthermore, according to the present invention, a novel polymer having sufficient adsorptivity to a metal such as a plating catalyst, and also excellent in polymerizability, a synthesis method thereof, a composition using the novel polymer, and lamination The body can be provided.

発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION

[0047] 以下、本発明を詳細に説明する。 [0047] Hereinafter, the present invention will be described in detail.

表面金属膜材料の作製方法、金属パターン材料の作製方法  Method for producing surface metal film material, method for producing metal pattern material

本発明の第 1の金属膜付基板の作製方法は、（al)基板上に、めっき触媒又はそ の前駆体と相互作用を形成する官能基を有し、且つ、該基板と直接化学結合したポ リマーからなるポリマー層を形成する工程と、（a2)該ポリマー層にめっき触媒又はそ の前駆体を付与する工程と、 (a3)該めっき触媒又はその前駆体に対してめつきを行 う工程と、を有し、前記ポリマー層が下記 1〜4の条件の全てを満たすことを特徴とす 条件 1 : 25°C— 50%相対湿度環境下における飽和吸水率が 0. 01〜； 10質量％ 条件 2 : 25°C— 95%相対湿度環境下における飽和吸水率が 0. 05〜20質量％ 条件 3 : 100°C煮沸水に 1時間浸漬した後の吸水率が 0. ；!〜 30質量％ 条件 4 : 25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置 後の表面接触角が 50〜 150度  In the first method for producing a substrate with a metal film of the present invention, (al) the substrate has a functional group that interacts with a plating catalyst or a precursor thereof, and is directly chemically bonded to the substrate. Forming a polymer layer composed of a polymer; (a2) applying a plating catalyst or a precursor thereof to the polymer layer; and (a3) attaching to the plating catalyst or a precursor thereof. And the polymer layer satisfies all of the following conditions 1 to 4: Condition 1: 25 ° C.—Saturated water absorption in a 50% relative humidity environment is 0.01 to 10; Mass% Condition 2: Saturated water absorption rate at 25 ° C-95% relative humidity is 0.05 to 20% by mass Condition 3: Water absorption rate after immersion in boiling water at 100 ° C for 1 hour is 0.; 30% by mass Condition 4: 25 ° C-50% relative humidity In a 5% L distilled water drop, the surface contact angle after standing for 15 seconds is 50 to 150 degrees

[0048] また、本発明の第 2の表面金属膜材料の作製方法は、（al ' )基板上に、シァノ基を 有し、且つ、該基板と直接化学結合したポリマーからなるポリマー層を形成する工程 と、（a2)該ポリマー層にめっき触媒又はその前駆体を付与する工程と、（a3)該めつ き触媒又はその前駆体に対してめつきを行う工程と、を有することを特徴とする。 [0048] Further, in the second method for producing a metal surface material of the present invention, a polymer layer made of a polymer having a cyano group and directly chemically bonded to the substrate is formed on the (al ') substrate. And (a2) a step of imparting a plating catalyst or a precursor thereof to the polymer layer, and (a3) a step of attaching the plating catalyst or the precursor thereof. And

[0049] 本発明の金属パターン材料の作製方法は、（a4)本発明の表面金属膜材料の作製 方法により得られた表面金属膜材料のめっき膜をパターン状にエッチングする工程 を有することを特徴とする。 つまり、金属パターン材料の作製方法は、前述の表面金属膜材料の作製方法にお ける（al)又は（al ' )、 （a2)、 （a3)工程を行った後、形成されためつき膜をパターン 状にエッチングする工程〔（a4)工程〕を行うものである。 [0049] The method for producing a metal pattern material of the present invention comprises (a4) a step of etching a plating film of a surface metal film material obtained by the method for producing a surface metal film material of the present invention into a pattern. And In other words, the metal pattern material is produced by performing the steps (al), (al ′), (a2), and (a3) in the method for producing the surface metal film material. The step of etching into a pattern [step (a4)] is performed.

[0050] 本発明の第 1の表面金属膜材料の作製方法、及び金属パターン材料の作製方法 において、上記 4つの条件を満たすポリマー層は、高温高湿下であっても吸水性が 低ぐまた、疎水性が高いものである。また、本発明の第 2の表面金属膜材料の作製 方法で形成されるポリマー層も、高温高湿下であっても吸水性が低ぐまた、疎水性 が高いものである。 [0050] In the method for producing the first surface metal film material and the method for producing the metal pattern material of the present invention, the polymer layer satisfying the above four conditions has low water absorption even under high temperature and high humidity. , Have high hydrophobicity. In addition, the polymer layer formed by the method for producing the second surface metal film material of the present invention has low water absorption and high hydrophobicity even under high temperature and high humidity.

また、基板に結合したポリマーからなるポリマー層にめっき触媒等を付与した後、こ れを用いてめっきを行うことでポリマー層との密着性に優れた金属膜を得ることができ これらの点から、得られた表面金属膜材料は、基板との密着性に優れた金属膜を 有し、更に、ポリマー層が湿度変化に応じて変化することがないため、湿度変化によ る密着力の変動が少ないものとなる。このような表面金属膜材料は、後述の金属バタ ーン材料の作製方法等に適用されて、電気配線用材料として用いられる他にも、電 磁波防止膜、シールド材料等に用いることができる。  In addition, a metal film having excellent adhesion to the polymer layer can be obtained by applying a plating catalyst or the like to the polymer layer composed of the polymer bonded to the substrate and then performing plating using the catalyst. The obtained surface metal film material has a metal film with excellent adhesion to the substrate, and the polymer layer does not change according to the humidity change. Will be less. Such a surface metal film material is applied to a method for producing a metal pattern material, which will be described later, and can be used as an electromagnetic wave prevention film, a shield material, etc., in addition to being used as an electric wiring material.

また、金属パターン材料の作製方法であれば、（a4)工程にて、基板全面に形成さ れためつき膜をパターン状にエッチングして金属パターンを得ることで、該金属バタ 一ンの非形成領域にこのポリマー層が露出した状態が形成されても、この露出した部 分は吸水することがなぐこれに起因する絶縁性の低下が起こらない。その結果、本 発明の金属パターン材料の作製方法において形成された金属パターン材料は、金 属パターンの非形成領域の絶縁信頼性に優れたものとなる。  Further, in the case of a method for producing a metal pattern material, in step (a4), the metal pattern is not formed by obtaining a metal pattern by etching the cover film formed on the entire surface of the substrate in a pattern. Even if the polymer layer is exposed in the region, the exposed portion does not absorb water and the insulation is not lowered. As a result, the metal pattern material formed in the method for producing the metal pattern material of the present invention has excellent insulation reliability in the non-formation region of the metal pattern.

[0051] 以下、本発明の第 1の表面金属膜材料の作製方法における 1〜4の各条件につい て説明する。 [0051] Hereinafter, each of the conditions 1 to 4 in the method for producing the first surface metal film material of the present invention will be described.

条件 1〜3における飽和吸水率及び吸水率は、以下の方法にて測定することができ まず、基板を減圧乾燥機内に放置し、基板内に含まれる水分を除去した後、条件 1 、 2の場合は、所望の温度及び湿度に設定された恒温恒湿槽内に放置し、条件 3の 場合は、 100°C煮沸水入りのウォーターバスに 1時間浸漬し、質量変化の測定によつ て飽和吸水率及び吸水率を測定する。ここで、条件 1、 2における飽和吸水率は、質 量が 24時間経過後も変化しなくなった時の吸水率を示している。別途、予め質量変 化が既知である前記基板上にポリマー層を形成した積層体についても、同様の操作 により積層体の飽和吸水率及び吸水率を測定することにより、基板の吸水率と積層 体の吸水率との差分によりポリマー層の吸水率を測定することができる。また、ポリマ 一層を基板上に付与せずに、シャーレなどを用いて、ポリマー層を構成するポリマー の単独膜を作製し、得られたポリマー単独膜を、上記の方法によって直接吸水率を 測定してもよい。 The saturated water absorption rate and water absorption rate under conditions 1 to 3 can be measured by the following method. First, the substrate is left in a vacuum dryer to remove moisture contained in the substrate, and then the conditions 1 and 2 If this is the case, leave it in a constant temperature and humidity chamber set to the desired temperature and humidity. In this case, immerse in a water bath with boiling water at 100 ° C for 1 hour, and measure the saturated water absorption and water absorption by measuring mass change. Here, the saturated water absorption rate under conditions 1 and 2 indicates the water absorption rate when the mass does not change after 24 hours. Separately, for a laminate in which a polymer layer is formed on the substrate whose mass change is known in advance, the water absorption rate of the substrate and the laminate are measured by measuring the saturated water absorption rate and the water absorption rate of the laminate in the same manner. The water absorption rate of the polymer layer can be measured by the difference from the water absorption rate. In addition, using a petri dish or the like without providing a polymer layer on the substrate, a single polymer film constituting the polymer layer was prepared, and the resulting single polymer film was directly measured for water absorption by the above method. May be.

[0052] 条件 4における接触角は、以下の方法にて測定することができる。  [0052] The contact angle in Condition 4 can be measured by the following method.

まず、基板上にポリマー層を形成した積層体を準備し、 25°C_50%相対湿度に設 定された恒温恒湿槽内で保管する。保管されたサンプルを、 25°C— 50%相対湿度 に調整された測定室内にて、表面接触角接触角測定装置（商品名： OCA20、 Data physics社製）を用いて、基板 (ポリマー層）上に 5 Lの蒸留水をシリンジから自動滴 下し、基板断面方向の画像を CCDカメラによってパソコンに取り込み、画像解析によ り基板 (ポリマー層）上の水滴の接触角度を数値計算する。  First, a laminate in which a polymer layer is formed on a substrate is prepared, and stored in a constant temperature and humidity chamber set at 25 ° C_50% relative humidity. Using a surface contact angle contact angle measurement device (trade name: OCA20, manufactured by Data physics) in a measurement chamber adjusted to 25 ° C—50% relative humidity, the stored sample is a substrate (polymer layer) 5 L of distilled water is automatically dropped from the syringe on the top, the image in the cross-sectional direction of the substrate is taken into a personal computer by a CCD camera, and the contact angle of the water droplet on the substrate (polymer layer) is numerically calculated by image analysis.

[0053] また、本発明においては、（al)工程で得られたポリマー層が、下記;！'〜 4'の条件 の全てを満たすことが好ましレ、態様である。 [0053] In the present invention, the polymer layer obtained in the step (al) is: It is preferable to satisfy all the conditions of “˜4”.

条件 1 ' : 25°C— 50%相対湿度環境下における飽和吸水率が 0. 0；!〜 5質量％ 条件 2' : 25°C— 95%相対湿度環境下における飽和吸水率が 0. 05〜； 10質量％ 条件 3' : 100°C煮沸水に 1時間浸漬した後の吸水率が 0. ；!〜 20質量％ 条件 4' : 25°C— 50%相対湿度環境下において、蒸留水 5 しを滴下し、 15秒静 置後の表面接触角が 55〜150度  Condition 1 ': 25 ° C—Saturated water absorption at 50% relative humidity is 0.0; 0 to 5% by mass Condition 2': 25 ° C—Saturated water absorption at 95% relative humidity is 0.05 ~; 10% by mass Condition 3 ': Water absorption after immersion in boiling water at 100 ° C for 1 hour is 0.;! ~ 20% by mass Condition 4': 25 ° C—distilled water at 50% relative humidity 5 The surface contact angle after standing for 15 seconds is 55 to 150 degrees.

[0054] ここで、上記 1〜4 (好ましくは;！'〜 4' )の条件を全て満たすポリマー層を得るため には、このポリマー層を構成するポリマーとして、吸水性が低いものや、疎水性のもの (親水性が低いもの）を用いる方法や、ポリマー層中に、吸水性を低下させる物質や 、疎水性を向上させるような物質を添加する方法、更には、ポリマー層を形成した後、 該ポリマー層を形成するポリマー分子を疎水化する反応性物質を含む溶液などに浸 漬させて、ポリマーとその反応性物質を反応させて疎水化するなど方法が挙げられる[0054] Here, in order to obtain a polymer layer satisfying all of the above conditions 1 to 4 (preferably;! 'To 4'), the polymer constituting the polymer layer may be a polymer having low water absorption or hydrophobicity. A method using a material having a low hydrophilicity (low hydrophilicity), a method of adding a substance that lowers water absorption or a substance that improves hydrophobicity to the polymer layer, and after forming the polymer layer Soak in a solution containing a reactive substance that hydrophobizes the polymer molecules forming the polymer layer. Examples of methods include soaking and hydrophobizing polymers and their reactive substances.

1S 吸水性や疎水性の制御の容易性の観点から、ポリマー層を構成するポリマーとし て、吸水性が低いものや、疎水性のもの（親水性が低いもの）を用いる方法を用いる ことが好ましい。 From the viewpoint of easy control of 1S water absorption and hydrophobicity, it is preferable to use a method using a polymer having a low water absorption or a hydrophobic polymer (low hydrophilicity) as the polymer constituting the polymer layer. .

[0055] まず、本発明の第 1の表面金属膜材料の作製方法における（al)〜（a3)の各工程 、及び、本発明の第 2の表面金属膜材料の作製方法における（al ' )〜（a3)の各ェ 程について説明する。  [0055] First, steps (al) to (a3) in the method for producing the first surface metal film material of the present invention, and (al ') in the method for producing the second surface metal film material of the present invention Each process of ~ (a3) will be explained.

[0056] (al)工程  [0056] (al) Process

本発明の第 1の表面金属膜材料の作製方法における（al)工程では、基板上に、 めっき触媒又はその前駆体と相互作用を形成する官能基（以下、単に、「相互作用 性基」と称する場合がある。）を有し、且つ、該基板と直接化学結合したポリマーから なるポリマー層を形成する。  In the (al) step in the first surface metal film material production method of the present invention, a functional group (hereinafter simply referred to as “interactive group”) that forms an interaction with the plating catalyst or its precursor on the substrate. And a polymer layer made of a polymer that is directly chemically bonded to the substrate.

このポリマー層は、前記 1〜4の条件を全て満たすことを要する。  This polymer layer is required to satisfy all the above conditions 1 to 4.

[0057] (al)工程は、基板上に、めっき触媒又はその前駆体と相互作用を形成する官能基 、及び重合性基を有するポリマーを直接化学結合させることにより行われることが好ま しい。 [0057] The step (al) is preferably performed by directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor on the substrate.

また、（al)工程が、（al— 1)基材上に、重合開始剤を含有する、又は重合開始可 能な官能基を有する重合開始層が形成された基板を作製する工程と、（al— 2)該重 合開始層に、相互作用性基を有し、且つ、該重合開始層と直接化学結合したポリマ 一からなるポリマー層を形成する工程であることも好ましい態様である。  In addition, the (al) step includes (al-1) a step of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a substrate; al-2) It is also a preferred embodiment that the polymerization initiating layer is a step of forming a polymer layer comprising a polymer having an interactive group and directly chemically bonded to the polymerization initiating layer.

また、上記 (al— 2)工程は、前記重合開始層上に、重合性基及び相互作用性基を 有するポリマーを接触させた後、エネルギーを付与することにより、前記基板表面全 体（重合開始層表面全体）に当該ポリマーを直接化学結合させる工程であることが好 ましい。  In the step (al-2), after the polymer having a polymerizable group and an interactive group is brought into contact with the polymerization initiation layer, energy is applied to the entire substrate surface (polymerization initiation). The process is preferably a process in which the polymer is directly chemically bonded to the entire surface of the layer.

[0058] 表面グラフト [0058] Surface graft

基板上におけるポリマー層の形成には、一般的な表面グラフト重合と呼ばれる手段 を用いる。グラフト重合とは、高分子化合物鎖上に活性種を与え、これによつて重合 を開始する別の単量体を更に重合させ、グラフト (接ぎ木）重合体を合成する方法で ある。特に、活性種を与える高分子化合物が固体表面を形成する時には、表面ダラ フト重合と呼ばれる。 A general method called surface graft polymerization is used to form the polymer layer on the substrate. Graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on the polymer compound chain and further polymerizing another monomer that initiates polymerization. is there. In particular, when the polymer compound that gives the active species forms a solid surface, this is called surface draft polymerization.

[0059] 本発明に適用される表面グラフト重合法としては、文献記載の公知の方法をいずれ も使用すること力できる。例えば、新高分子実験学 10、高分子学会編、 1994年、共 立出版 (株)発行、 pl35には表面グラフト重合法として光グラフト重合法、プラズマ照 射グラフト重合法が記載されている。また、吸着技術便覧、 NTS (株）、竹内監修、 19 99. 2発行、 p203、 p695には、 γ線、電子線などの放射線照射グラフト重合法が記 載されている。  [0059] As the surface graft polymerization method applied to the present invention, any known method described in the literature can be used. For example, New Polymer Experiment 10, edited by Polymer Society of Japan, 1994, published by Kyoritsu Shuppan Co., Ltd., pl35 describes photograft polymerization and plasma irradiation graft polymerization as surface graft polymerization methods. In addition, the adsorption technology handbook, NTS Co., Ltd., supervised by Takeuchi, published 19 99.2, p203, p695, describes irradiation-induced graft polymerization methods such as gamma rays and electron beams.

光グラフト重合法の具体的方法の例としては、特開昭 63— 92658号公報、特開平 10— 296895号公報及び特開平 11— 119413号公報に記載の方法が挙げられる Specific examples of the photograft polymerization method include the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413.

〇 Yes

[0060] 本発明の表面金属膜材料の作製方法におけるポリマー層を形成する際には、上記 の表面グラフト法以外にも、高分子化合物鎖の末端に、トリアルコキシシリル基、イソ シァネート基、アミノ基、水酸基、カルボキシル基などの反応性官能基を付与し、これ と基板表面に存在する官能基とのカップリング反応により結合させる方法を適用する ことあでさる。  [0060] When forming the polymer layer in the method for producing a surface metal film material of the present invention, in addition to the surface grafting method described above, a trialkoxysilyl group, isocyanate group, amino group is added to the end of the polymer compound chain. It is possible to apply a method in which a reactive functional group such as a group, a hydroxyl group, or a carboxyl group is added and bonded by a coupling reaction between the functional group and the functional group present on the substrate surface.

これらの方法の中でも、より多くのグラフトポリマーを生成する観点からは、光グラフ ト重合法、特に、 UV光による光グラフト重合法を用いてポリマー層を形成することが 好ましい。  Among these methods, from the viewpoint of generating more graft polymers, it is preferable to form a polymer layer using a photograft polymerization method, particularly a photograft polymerization method using UV light.

[0061] 基板  [0061] Substrate

本発明の表面金属膜材料の作製方法における「基板」とは、その表面が、めっき触 媒又はその前駆体と相互作用を形成する官能基を有するポリマーが直接化学結合 した状態を形成しうる機能を有するものであり、基材自体がこのような表面特性を有し て基板を構成するものであってもよぐまた、基材上に別途中間層（例えば、後述する 重合開始層）を設け、該中間層がこのような特性を有して基板を構成するものであつ てもよい。  The “substrate” in the method for producing a surface metal film material of the present invention is a function that can form a state in which a polymer having a functional group that interacts with a plating catalyst or a precursor thereof is directly chemically bonded. The substrate itself may have such surface characteristics to constitute the substrate, and a separate intermediate layer (for example, a polymerization initiation layer described later) is provided on the substrate. The intermediate layer may have such characteristics to constitute the substrate.

[0062] 基材、基板 [0062] Base material, substrate

本発明に使用される基材は、寸度的に安定な板状物であることが好ましぐその例 には、紙、プラスチック（例えば、ポリエチレン、ポリプロピレン、ポリスチレン等）がラミ ネートされた紙、金属板 (例えば、アルミニウム、亜鉛、銅等）、プラスチックフィルム（ 例えば、二酢酸セルロース、三酢酸セルロース、プロピオン酸セルロース、酪酸セノレ ロース、酢酸セノレロース、硝酸セノレロース、ポリエチレンテレフタレート、ポリエチレン 、ポリスチレン、ポリプロピレン、ポリカーボネート、ポリビュルァセタール、ポリイミド、 エポキシ、ビスマレインイミド樹脂、ポリフエ二レンオキサイド、液晶ポリマー、ポリテトラ フルォロエチレン等）、上記の如き金属がラミネート若しくは蒸着された紙又はプラス チックフィルム等が含まれる。本発明に使用される基材としては、エポキシ樹脂、又は ポリイミド樹脂が好ましい。 An example of the substrate used in the present invention is preferably a dimensionally stable plate. Paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, propion) Acid cellulose, butanolic acid senololose, acetylenic acetate, senorelose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polybulacetal, polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.) In addition, paper or plastic film on which a metal as described above is laminated or vapor-deposited are included. As a base material used for this invention, an epoxy resin or a polyimide resin is preferable.

なお、これらの基材表面が、めっき触媒又はその前駆体と相互作用を形成する官 能基を有するポリマーが直接化学結合した状態を形成しうる機能を有している場合 には、その基材そのものを基板として用いてもよい。  If these substrate surfaces have a function capable of forming a state in which a polymer having a functional group that interacts with the plating catalyst or its precursor has a direct chemical bond, the substrate It may be used as a substrate.

[0063] 本発明における基板として、特開 2005— 281350号公報の段落番号 [0028]〜[ 0088]に記載の重合開始部位を骨格中に有するポリイミドを含む基材を用いることも できる。 [0063] As the substrate in the present invention, a base material containing polyimide having a polymerization initiation site in the skeleton described in paragraphs [0028] to [0088] of JP-A-2005-281350 can also be used.

[0064] また、本発明の金属パターン材料の作製方法により得られた金属パターン材料は、 半導体パッケージ、各種電気配線基板等に適用することができる。このような用途に 用いる場合は、以下に示す、絶縁性樹脂を含んだ基板を用いることが好ましい。具 体的には、絶縁性樹脂からなる基板、又は、絶縁性樹脂からなる層を基材上に有す る基板を用いることが好ましレ、。  [0064] The metal pattern material obtained by the method for producing a metal pattern material of the present invention can be applied to a semiconductor package, various electric wiring boards, and the like. When used in such applications, it is preferable to use a substrate containing an insulating resin as shown below. Specifically, it is preferable to use a substrate made of an insulating resin or a substrate having a layer made of an insulating resin on a base material.

[0065] 絶縁性樹脂からなる基板、絶縁性樹脂からなる層を得る場合には、公知の絶縁性 樹脂組成物が用いられる。この絶縁性樹脂組成物には、主成分たる樹脂に加え、 目 的に応じて種々の添加物を併用することができる。例えば、絶縁層の強度を高める目 的で、多官能のアタリレートモノマーを添加する、絶縁体層の強度を高め、電気特性 を改良する目的で、無機、若しくは有機の粒子を添加する、などの手段をとることもで きる。  [0065] In the case of obtaining a substrate made of an insulating resin and a layer made of an insulating resin, a known insulating resin composition is used. In addition to the resin as the main component, various additives can be used in combination with the insulating resin composition depending on the purpose. For example, for the purpose of increasing the strength of the insulating layer, a polyfunctional acrylate monomer is added, or for the purpose of increasing the strength of the insulating layer and improving the electrical characteristics, inorganic or organic particles are added, etc. Measures can also be taken.

なお、本発明における「絶縁性樹脂」とは、公知の絶縁膜や絶縁層に使用しうる程 度の絶縁性を有する樹脂であることを意味するものであり、完全な絶縁体でなレ、もの であっても、 目的に応じた絶縁性を有する樹脂であれば、本発明に適用しうる。 The “insulating resin” in the present invention means a resin having a degree of insulation that can be used for a known insulating film or insulating layer. thing However, any resin having an insulating property according to the purpose can be applied to the present invention.

[0066] 絶縁性樹脂は、熱硬化性樹脂でも熱可塑性樹脂でもまたそれらの混合物でもよ!/、 。具体的には、例えば、熱硬化性樹脂としては、エポキシ樹脂、フエノール樹脂、ポリ イミド樹脂、ポリエステル樹脂、ビスマレイミド樹脂、ポリオレフイン系樹脂、イソシァネ ート系樹脂等が挙げられる。 [0066] The insulating resin may be a thermosetting resin, a thermoplastic resin, or a mixture thereof! /. Specific examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, and the like.

エポキシ樹脂としては、例えば、クレゾールノポラック型エポキシ樹脂、ビスフエノー ル A型エポキシ樹脂、ビスフエノール F型エポキシ樹脂、フエノールノポラック型ェポ キシ樹脂、アルキルフエノールノポラック型エポキシ樹脂、ビフエノール F型エポキシ 樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジェン型エポキシ樹脂、フエノール 類とフエノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物、トリグ リシジルイソシァヌレート、脂環式エポキシ樹脂等が挙げられる。これらは、単独で用 いてもよぐ 2種以上併用してもよい。それにより、耐熱性等に優れるものとなる。  Examples of the epoxy resin include cresol nopolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol nopolak type epoxy resin, alkylphenol nopolac type epoxy resin, biphenol F type epoxy resin. , Naphthalene type epoxy resins, dicyclopentagen type epoxy resins, epoxidized products of condensates of phenols with aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resins and the like. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.

ポリオレフイン系樹脂としては、例えば、ポリエチレン、ポリスチレン、ポリプロピレン、 ポリイソブチレン、ポリブタジエン、ポリイソプレン、シクロォレフイン系樹脂、これらの 樹脂の共重合体等が挙げられる。  Examples of the polyolefin resin include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, a cycloolefin resin, and copolymers of these resins.

[0067] 熱可塑性樹脂としては、例えば、フエノキシ樹脂、ポリエーテルスルフォン、ポリスル フォン、ポリフエ二レンスルフォン、ポリフエ二レンサルファイド、ポリフエニルエーテノレ、 ポリエーテルイミド等が挙げられる。 [0067] Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ethereol, polyether imide, and the like.

その他の熱可塑性樹脂としては、 1 , 2—ビス（ビュルフエ二レン）ェタン樹脂（1 , 2 -Bis (vinylphenyl) ethane)、若しくはこれとポリフエ二レンエーテル樹脂との変性 樹脂（天羽悟ら、 Journal of Applied Polymer Science VoL92， 1252-1258(2004)に記載 )、液晶性ポリマー（具体的には、クラレ製のベタスターなど）、フッ素樹脂（PTFE)な どが挙げられる。  Other thermoplastic resins include 1,2-bis (buhlylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or modified resins of this with polyphenylene ether resins (Satoru Ama et al., Journal of Applied Polymer Science VoL92, 1252-1258 (2004)), liquid crystalline polymers (specifically, Kuraray Betastar, etc.), fluororesin (PTFE), and the like.

[0068] 熱可塑性樹脂と熱硬化性樹脂とは、それぞれ単独で用いてもよ!/、し、 2種以上併用 してもよい。これはそれぞれの欠点を補いより優れた効果を発現する目的で行われる 。例えば、ポリフエ二レンエーテル (PPE)などの熱可塑性樹脂は熱に対しての耐性 が低いため、熱硬化性樹脂などとのァロイ化が行われている。たとえば、 PPEとェポ キシ、トリアリルイソシァネートとのァロイ化、或いは重合性官能基を導入した PPE樹 脂とそのほかの熱硬化性樹脂とのァロイ化として使用される。またシァネートエステル は熱硬化性の中ではもつとも誘電特性の優れる樹脂である力 それ単独で使用され ることは少なく、エポキシ樹脂、マレイミド樹脂、熱可塑性樹脂などの変性樹脂として 使用される。これらの詳細に関しては、 "電子技術" 2002/9号、 P35に記載されて いる。また、熱硬化性樹脂として、エポキシ樹脂及び/又はフエノール樹脂を含み、 熱可塑性樹脂としてフエノキシ樹脂及び/又はポリエーテルスルフォン (PES)を含 むものも誘電特性を改善するために使用される。 [0068] The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is done for the purpose of compensating each defect and producing a better effect. For example, thermoplastic resins such as polyphenylene ether (PPE) have low resistance to heat, and are therefore alloyed with thermosetting resins. For example, alloying PPE with epoxy or triallyl isocyanate, or a PPE tree with a polymerizable functional group introduced Used as alloying of fat with other thermosetting resins. Cyanate ester is a resin that has excellent dielectric properties in thermosetting properties, but is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. These details are described in "Electronic Technology" No. 2002/9, P35. In addition, a thermosetting resin containing an epoxy resin and / or a phenol resin and a thermoplastic resin containing a phenoxy resin and / or polyether sulfone (PES) are also used for improving the dielectric properties.

[0069] 絶縁性樹脂組成物には、架橋を進めるために重合性の二重結合を有する化合物 のようなもの、具体的には、アタリレート、メタタリレート化合物を含有していてもよぐ 特に多官能のものが好ましい。そのほか、重合性の二重結合を有する化合物として、 熱硬化性樹脂、若しくは熱可塑性樹脂、例えば、エポキシ樹脂、フエノール樹脂、ポ リイミド樹脂、ポリオレフイン樹脂、フッ素樹脂等に、メタクリル酸やアクリル酸等を用い 、樹脂の一部を (メタ）アクリル化反応させた樹脂を用いてもょレ、。  [0069] The insulating resin composition may contain a compound having a polymerizable double bond in order to promote crosslinking, specifically, an acrylate or metatalylate compound. Sensory ones are preferred. In addition, as a compound having a polymerizable double bond, a thermosetting resin or a thermoplastic resin such as an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, methacrylic acid, acrylic acid, or the like is used. Use a resin in which a part of the resin is (meth) acrylated.

[0070] 本発明における絶縁性樹脂組成物には、樹脂被膜の機械強度、耐熱性、耐候性、 難燃性、耐水性、電気特性などの特性を強化するために、樹脂と他の成分とのコン ポジット (複合素材)も使用することができる。複合化するのに使用される材料としては 、紙、ガラス繊維、シリカ粒子、フエノール樹脂、ポリイミド樹脂、ビスマレイミドトリアジ ン樹脂、フッ素樹脂、ポリフエ二レンオキサイド樹脂などを挙げることができる。  [0070] The insulating resin composition according to the present invention includes a resin and other components in order to enhance the properties of the resin film such as mechanical strength, heat resistance, weather resistance, flame retardancy, water resistance, and electrical properties. Other composites can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluororesin, and polyphenylene oxide resin.

[0071] 更に、この絶縁性樹脂組成物には必要に応じて一般の配線板用樹脂材料に用レ、 られる充填剤、例えば、シリカ、アルミナ、クレー、タルク、水酸化アルミニウム、炭酸力 ルシゥムなどの無機フィラー、硬化エポキシ樹脂、架橋べンゾグアナミン樹脂、架橋 アクリルポリマーなどの有機フィラーを一種又は二種以上配合してもよい。中でも、充 填材としてはシリカを用いることが好ましレ、。  [0071] Further, the insulating resin composition can be used for a general resin material for a wiring board, if necessary, for example, silica, alumina, clay, talc, aluminum hydroxide, carbonic acid, ruthenium, etc. Inorganic fillers, cured epoxy resins, cross-linked benzoguanamine resins, cross-linked acrylic polymers and other organic fillers may be used alone or in combination. Of these, silica is the preferred filler.

また、更に、この絶縁性樹脂組成物には、必要に応じて着色剤、難燃剤、接着性付 与剤、シランカップリング剤、酸化防止剤、紫外線吸収剤、などの各種添加剤を一種 又は二種以上添加してもよレ、。  Furthermore, the insulating resin composition may contain various additives such as a colorant, a flame retardant, an adhesive agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. You can add two or more.

[0072] これらの材料を絶縁性樹脂組成物に添加する場合は、いずれも、樹脂に対して、 1 〜200質量％の範囲で添加されることが好ましぐより好ましくは 10〜80質量％の範 囲で添加される。この添加量が、 1質量％未満である場合は、上記の特性を強化する 効果がなぐまた、 200質量％を超えると場合には、樹脂特有の強度などの特性が低 下する。 [0072] When these materials are added to the insulating resin composition, it is preferable to add them in the range of 1 to 200% by mass with respect to the resin, more preferably 10 to 80% by mass. Range of Added in a box. If the amount added is less than 1% by mass, the effect of enhancing the above properties is not obtained. If the amount added exceeds 200% by mass, properties such as strength peculiar to the resin are deteriorated.

[0073] このような用途に用いる場合の基板として、具体的には、 1GHzにおける誘電率（比 誘電率）が 3. 5以下である絶縁性樹脂からなる基板である力、、又は、該絶縁性樹脂 力もなる層を基材上に有する基板であることが好ましい。また、 1GHzにおける誘電 正接が 0. 01以下である絶縁性樹脂からなる基板である力、、又は、該絶縁性樹脂か らなる層を基材上に有する基板であることが好ましい。  [0073] As a substrate for use in such applications, specifically, the force which is a substrate made of an insulating resin having a dielectric constant (relative dielectric constant) at 1 GHz of 3.5 or less, or the insulation It is preferable that the substrate has a layer on the base material that also has a strong resin strength. Further, a force that is a substrate made of an insulating resin having a dielectric loss tangent at 1 GHz of 0.01 or less, or a substrate having a layer made of the insulating resin on a base material is preferable.

絶縁性樹脂の誘電率及び誘電正接は、常法により測定することができる。例えば、 「第 18回エレクトロニクス実装学会学術講演大会要旨集」、 2004年、 pi 89、に記載 の方法に基づき、空洞共振器摂動法 (例えば、極薄シート用 ε r、 tan δ測定器、キ 一コム株式会社製）を用いて測定することができる。  The dielectric constant and dielectric loss tangent of the insulating resin can be measured by a conventional method. For example, the cavity resonator perturbation method (for example, ε r, tan δ measuring device for ultra-thin sheet, key, based on the method described in “18th Annual Meeting of the Japan Institute of Electronics Packaging”, pi 89, 2004. It can be measured using Ichicom Co., Ltd.).

このように、本発明においては誘電率や誘電正接の観点から絶縁樹脂材料を選択 することも有用である。誘電率が 3. 5以下であり、誘電正接が 0. 01以下の絶縁性樹 脂としては、液晶ポリマー、ポリイミド樹脂、フッ素樹脂、ポリフエ二レンエーテル樹脂、 シァネートエステル樹脂、ビス（ビスフエ二レン）ェタン樹脂などが挙げられ、更にそれ らの変性樹脂も含まれる。  Thus, in the present invention, it is also useful to select an insulating resin material from the viewpoint of dielectric constant and dielectric loss tangent. Insulating resins having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.01 or less include liquid crystal polymers, polyimide resins, fluororesins, polyphenylene ether resins, cyanate ester resins, bis (bisphenylenes). ) Ethane resins and the like, and further modified resins thereof.

[0074] 本発明に用いられる基板は、半導体パッケージ、各種電気配線基板等への用途を 考慮すると、表面凹凸が 500nm以下であることが好ましぐより好ましくは lOOnm以 下、更に好ましくは 50nm以下、最も好ましくは 20nm以下である。この基板の表面凹 凸（中間層や重合開始層が設けられている場合はその層の表面凹凸）が小さくなる ほど、得られた金属パターン材料を配線等に適用した場合に、高周波送電時の電気 損失が少なくなり好ましい。  [0074] The substrate used in the present invention has surface irregularities of preferably 500 nm or less, more preferably lOOnm or less, and even more preferably 50 nm or less, in consideration of applications to semiconductor packages, various electric wiring boards, and the like. Most preferably, it is 20 nm or less. When the surface irregularity of this substrate (surface irregularity of the layer when an intermediate layer or polymerization initiation layer is provided) becomes smaller, when the obtained metal pattern material is applied to wiring or the like, It is preferable because electric loss is reduced.

[0075] 本発明においては、基板が板状物、例えば、樹脂フィルム（プラスチックフィルム）で あれば、その両面に（al)工程を施すことで、樹脂フィルムの両面にポリマー層を形 成すること力 Sできる（本発明の第 3の表面金属膜材料の作製方法における（al")ェ 程)。  [0075] In the present invention, if the substrate is a plate-like material, for example, a resin film (plastic film), the polymer layer is formed on both surfaces of the resin film by performing an (al) process on both surfaces. (In the method for producing the third surface metal film material of the present invention, (al ")).

このように樹脂フィルム（基板）の両面にポリマー層が形成された場合には、更に、 後述する（a2)工程、及び (a3)工程を行うことで、両面に金属膜が形成された表面金 属膜材料を得ることができる。 When the polymer layer is formed on both sides of the resin film (substrate) in this way, By performing the steps (a2) and (a3) described later, a surface metal film material having a metal film formed on both surfaces can be obtained.

[0076] 本発明において、基板表面に活性種を与え、それを起点としてグラフトポリマーを 生成させる表面グラフト重合法を用いる場合、グラフトポリマーの生成に際しては、基 材上に、重合開始剤を含有する、又は重合開始可能な官能基を有する重合開始層 を形成した基板を用いることが好ましい。この基板を用いることで、活性点を効率よく 発生させ、より多くのグラフトポリマーを生成させることができる。  In the present invention, when a surface graft polymerization method is used in which an active species is given to the substrate surface and a graft polymer is generated starting from the active species, a polymerization initiator is contained on the base material when the graft polymer is generated. Alternatively, it is preferable to use a substrate on which a polymerization initiating layer having a functional group capable of initiating polymerization is formed. By using this substrate, active sites can be generated efficiently and more graft polymers can be generated.

以下、本発明における重合開始層について説明する。なお、基材が板状物であれ ば、その両面に重合開始層を形成してもよい。  Hereinafter, the polymerization initiation layer in the present invention will be described. If the substrate is a plate-like material, a polymerization initiating layer may be formed on both sides thereof.

[0077] 重合開始層  [0077] Polymerization initiation layer

本発明における重合開始層としては、高分子化合物と重合開始剤とを含む層や、 重合性化合物と重合開始剤とを含む層、重合開始可能な官能基を有する層が挙げ られる。  Examples of the polymerization initiating layer in the present invention include a layer containing a polymer compound and a polymerization initiator, a layer containing a polymerizable compound and a polymerization initiator, and a layer having a functional group capable of initiating polymerization.

本発明における重合開始層は、必要な成分を、溶解可能な溶媒に溶解し、塗布な どの方法で基材表面に設け、加熱又は光照射により硬膜することで、形成することが できる。  The polymerization initiating layer in the present invention can be formed by dissolving the necessary components in a solvent that can be dissolved, providing the components on the surface of the substrate by a method such as coating, and hardening by heating or light irradiation.

[0078] 本発明における重合開始層に用いられる化合物としては、基材との密着性が良好 であり、且つ、活性光線照射などのエネルギー付与により、活性種を発生するもので あれば特に制限なく用いることができる。具体的には、多官能モノマーや分子内に重 合性基を有する疎水性ポリマーと、重合開始剤とを混合したものが用いることができ  [0078] The compound used in the polymerization initiation layer in the present invention is not particularly limited as long as it has good adhesion to the substrate and generates active species by applying energy such as irradiation with actinic rays. Can be used. Specifically, a mixture of a polyfunctional monomer or a hydrophobic polymer having a polymerizable group in the molecule and a polymerization initiator can be used.

[0079] このような分子内に重合性基を有する疎水性ポリマーとしては、具体的には、ポリブ タジェン、ポリイソプレン、ポリペンタジェンなどのジェン系単独重合体、ァリル (メタ） アタリレー卜、 2—ァリルォキシェチルメタクリレー卜などのァリル基含有モノマーの単 独重合体； [0079] Specific examples of the hydrophobic polymer having a polymerizable group in the molecule include gen-based homopolymers such as polybutaene, polyisoprene, and polypentagen, —Homopolymers of aryl-containing monomers such as aryloxetyl methacrylate

ブタジエン、イソプレン、ペンタジェンなどのジェン系単量体又はァリル基含有モノ マーを構成単位として含む、スチレン、 （メタ）アクリル酸エステル、 （メタ）アタリロニトリ ルなどの二元又は多元共重合体； 不飽和ポリエステル、不飽和ポリエポキシド、不飽和ポリアミド、不飽和ポリアクリル、 高密度ポリエチレンなどの分子中に炭素 炭素二重結合を有する線状高分子又はBinary or multi-component copolymers such as styrene, (meth) acrylic acid ester, (meth) atrylonitrile, etc., containing gen-based monomers such as butadiene, isoprene and pentagene or aryl group-containing monomers as constituent units; Linear polymer having carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, high density polyethylene, etc.

3次元高分子類；などが挙げられる。 Three-dimensional polymers; and the like.

なお、本明細書では、「アクリル、メタクリル」の双方或いはいずれかを指す場合、「（ メタ）アクリル」と表記することがある。  In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.

これらの重合性化合物の含有量は、重合性層中、固形分で 10〜； 100質量％の範 囲が好ましぐ 10〜80質量％の範囲が特に好ましい。  The content of these polymerizable compounds is particularly preferably in the range of 10 to 80% by mass, preferably in the range of 10 to;

[0080] 重合開始層には、エネルギー付与により重合開始能を発現させるための重合開始 剤を含有する。ここで用いられる重合開始剤は、所定のエネルギー、例えば、活性光 線の照射、加熱、電子線の照射などにより、重合開始能を発現し得る公知の熱重合 開始剤、光重合開始剤などを、 目的に応じて、適宜選択して用いることができる。中 でも、光重合を利用することが製造適性の観点から好適であり、このため、光重合開 始剤を用いることが好ましい。 [0080] The polymerization initiation layer contains a polymerization initiator for expressing the polymerization initiation ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit a polymerization initiating ability by predetermined energy, for example, irradiation with active light beam, heating, electron beam irradiation, and the like. Depending on the purpose, it can be appropriately selected and used. Among these, it is preferable to use photopolymerization from the viewpoint of production suitability, and therefore it is preferable to use a photopolymerization initiator.

光重合開始剤は、照射される活性光線に対して活性であり、これを含む重合開始 層から表面グラフト重合が可能なものであれば、特に制限はなぐ例えば、ラジカノレ 重合開始剤、ァニオン重合開始剤、カチオン重合開始剤などを用いることができるが 、扱い易さ、反応性の観点からは、ラジカル重合開始剤、カチオン重合開始剤が好ま しぐ更に、ラジカル重合開始剤が好ましい。  The photopolymerization initiator is not particularly limited as long as it is active with respect to the irradiated actinic ray and can be surface-grafted from the polymerization initiation layer containing the photopolymerization initiator, for example, a radiocanole polymerization initiator or an anion polymerization starter. An agent, a cationic polymerization initiator, and the like can be used. From the viewpoint of ease of handling and reactivity, a radical polymerization initiator and a cationic polymerization initiator are preferred, and a radical polymerization initiator is preferred.

[0081] そのような光重合開始剤としては、具体的には、例えば、 p tert ブチルトリクロ口 ァセトフエノン、 2, 2 'ージエトキシァセトフエノン、 2—ヒドロキシー2—メチノレー 1ーフ ェニルプロパン一 1—オンの如きァセトフエノン類；ベンゾフエノン（4, 4，一ビスジメチ ノレアミノべンゾフエノン、 2—クロ口チォキサントン、 2—メチルチオキサントン、 2—ェチ ノレチォキサントン、 2—イソプロピルチォキサントン、の如きケトン類；ベンゾイン、ベン ゾインメチノレエーテノレ、ベンゾインイソプロピノレエーテノレ、ベンゾインイソプ、チノレエ一 テノレの如きべンゾインエーテノレ類；ペンジノレジメチノレケターノレ、ヒドロキシシクロへキ シルフェニルケトンの如きべンジルケタール類；トリフエニルスルホニゥムクロライド、ト リフエニノレスノレホニゥムペンタフノレオロフォスフェートなどのスノレホニゥム塩、ジフエ二 ノレョードニゥムクロライド、ジフエ二ルョードニゥムサルフェートなどのョードニゥム塩な どが挙げられる。 [0081] Specific examples of such a photopolymerization initiator include, for example, p tert butyl trichloroacetophenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methinoleyl 1-phenylpropane. Acetofenones such as 1-one; Ketones such as benzophenone (4, 4, 1 bisdimethinoreaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthiorexanthone, 2-isopropylthioxanthone; Benzoin etherenoles such as benzoin, benzoin methinoreethenole, benzoin isopropinoleethenore, benzoin isop, chinolee tenole; penzinoresimethinoreketanol, and hydroxycyclohexyl phenyl ketone Nilketals; triphenylsulfonium chloride , A Yodoniumu salts such as door Lihue Nino less Norre Honi ©-time Sunorehoniumu salt such as a pen tough Norre Oro phosphate, Jifue two Norre ® over Denis © skeleton ride, Jifue two Ruyo over Denis © beam sulfate And so on.

重合開始剤の含有量は、重合開始層中、固形分で 0. ；!〜 70質量％の範囲が好ま しぐ；!〜 40質量％の範囲が特に好ましい。  The content of the polymerization initiator is preferably in the range of 0.;! To 70% by mass in solid content in the polymerization initiator layer; particularly preferably in the range of!

[0082] 上記重合性化合物及び重合開始剤を塗布する際に用いる溶媒は、それらの成分 が溶解するものであれば特に制限されない。乾燥の容易性、作業性の観点からは、 沸点が高すぎない溶媒が好ましぐ具体的には、沸点 40°C〜150°C程度のものを選 択すればよい。 [0082] The solvent used in applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferred. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.

具体的には、アセトン、メチルェチルケトン、シクロへキサン、酢酸ェチル、テトラヒド 口フラン、トノレエン、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノ ェチノレエーテノレ、エチレングリコーノレジメチノレエーテノレ、プロピレングリコーノレモノメ チルエーテル、プロピレングリコールモノェチルエーテル、ァセチルアセトン、シクロ へキサノン、メタノール、エタノール、 1ーメトキシー2—プロパノール、 3—メトキシプロ ノ ノ一ノレ、ジエチレング!;コーノレモノメチノレエーテノレ、ジエチレング！;コーノレモノェチ ノレエーテノレ、ジエチレングリコーノレジメチノレエーテノレ、ジエチレングリコーノレジェチノレ エーテノレ、プロピレングリコーノレモノメチノレエーテノレアセテート、プロピレングリコーノレ モノェチルエーテルアセテート、 3—メトキシプロピルアセテートなどが挙げられる。 これらの溶媒は、単独或いは混合して使用することができる。そして塗布溶液中の 固形分の濃度は、 2〜50質量％が適当である。  Specific examples include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, tonoleene, ethylene glycol monomethino ethenore, ethylene glycol monomethino ethenore, ethylene glyconoresin methino rea. Tenole, Propylene glycol monomethyl ether, Propylene glycol monoethyl ether, Acetyl acetone, Cyclohexanone, Methanol, Ethanol, 1-Methoxy-2-propanol, 3-Methoxyprononore, Diethylene glycol !; Noreetenore, Diethylenegu! Cornole monoethylenoate, diethyleneglyconoresimethinoleatenore, diethyleneglycolenojetinole etenore, propylene glycolenomonomethinoatenole acetate, propylene glycolenole monoethyl ether acetate, 3-methoxypropyl acetate and the like. These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

[0083] 重合開始層を基材上に形成する場合の塗布量は、十分な重合開始能の発現、及 び、膜性を維持して膜剥がれを防止するといつた観点からは、乾燥後の質量で、 0. ；!〜 20g/m2力 S好ましく、 0. ；!〜 15g/m2がより好ましぐ 0. ；!〜 2g/m2が更に好ま しい。 [0083] The coating amount when the polymerization initiating layer is formed on the substrate is such that the sufficient polymerization initiating ability is exhibited, and from the viewpoint of preventing film peeling by maintaining film properties, By weight, 0.;! To 20 g / m 2 force S preferred, 0.;! To 15 g / m 2 more preferred 0.;! To 2 g / m 2 more preferred.

[0084] 本発明においては、上記のように、基材上に上記の重合開始層形成用の組成物を 塗布などにより配置し、溶剤を除去することにより成膜させて重合開始層を形成する 1S この時、加熱及び/又は光照射を行って硬膜することが好ましい。特に、加熱に より乾燥した後、光照射を行って予備硬膜しておくと、重合性化合物のある程度の硬 化が予め行なわれるので、重合開始層上にグラフトポリマーが生成した後に重合開 始層ごと脱落するとレ、つた事態を効果的に抑制し得るため好まし!/、。 加熱温度と時間は、塗布溶剤が充分乾燥し得る条件を選択すればよいが、製造適 正の点からは、温度が 100°C以下、乾燥時間は 30分以内が好ましぐ乾燥温度 40 〜80°C、乾燥時間 10分以内の範囲の加熱条件を選択することがより好ましい。 [0084] In the present invention, as described above, the composition for forming a polymerization initiation layer is disposed on a base material by coating or the like, and a film is formed by removing the solvent to form a polymerization initiation layer. 1S At this time, it is preferable to harden by heating and / or light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is preliminarily cured to some extent, so that the polymerization starts after the graft polymer is formed on the polymerization initiation layer. If you drop off the layer, it is preferable because you can effectively suppress the situation! The heating temperature and time may be selected so that the coating solvent can be sufficiently dried, but from the point of production suitability, the temperature is 100 ° C or less and the drying time is preferably within 30 minutes. It is more preferable to select heating conditions in the range of 80 ° C and drying time within 10 minutes.

[0085] 加熱乾燥後に所望により行われる光照射は、後述するグラフトポリマーの生成反応 に用いる光源を用いることができる。引き続き行われるグラフトポリマー生成工程にお いて、エネルギー付与により発生する重合開始層の活性点と、グラフトポリマーの生 成を阻害しなレ、とレ、う観点からは、重合開始層中に存在する重合開始剤が重合性化 合物を硬化する際にラジカル重合しても、完全に消費しない程度に光照射することが 好ましい。光照射時間については、光源の強度により異なる力 一般的には 30分以 内であることが好ましい。このような予備硬化の目安としては、溶剤洗浄後の膜残存 率が 80%以下となり、且つ、予備硬化後の開始剤残存率が 1%以上であることが、 挙げられる。 [0085] Light irradiation performed as desired after heat-drying can be performed using a light source used for a graft polymer formation reaction described later. In the subsequent graft polymer generation step, the active point of the polymerization initiating layer generated by the application of energy and the fact that it does not inhibit the formation of the graft polymer are present in the polymerization initiating layer. Even if radical polymerization is performed when the polymerization initiator cures the polymerizable compound, it is preferable to irradiate with light to such an extent that it is not completely consumed. The light irradiation time varies depending on the intensity of the light source. In general, it is preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent cleaning is 80% or less and the initiator remaining rate after pre-curing is 1% or more.

[0086] また、上記の重合性化合物及び重合開始剤を含有する重合開始層以外に、特開 2 004— 161995公報に記載の重合開始基が側鎖にペンダントしてなるポリマーを用 いた重合開始層も好ましい。このポリマーは、具体的には、側鎖に重合開始能を有 する官能基 (重合開始基)及び架橋性基を有するポリマー（以下、重合開始ポリマー と称する。）であり、このポリマーにより、ポリマー鎖に結合した重合開始基を有し、か つ、そのポリマー鎖が架橋反応により固定化された形態の重合開始層を形成するこ と力 Sできる。  [0086] In addition to the polymerization initiating layer containing the polymerizable compound and the polymerization initiator, polymerization initiation using a polymer in which a polymerization initiating group described in JP-A-20004-161995 is pendant on a side chain is used. A layer is also preferred. Specifically, this polymer is a polymer having a functional group (polymerization initiating group) having a polymerization initiating ability in the side chain and a crosslinkable group (hereinafter referred to as a polymerization initiating polymer). It is possible to form a polymerization initiating layer having a polymerization initiating group bonded to a chain and having the polymer chain immobilized by a crosslinking reaction.

このようにして形成される重合開始層も、本願の重合開始層として好適である。  The polymerization initiating layer thus formed is also suitable as the polymerization initiating layer of the present application.

[0087] ここで用いられる重合開始ポリマーは、特開 2004— 161995号公報の段落番号〔[0087] The polymerization initiating polymer used here is the paragraph number of JP 2004-161995 A [

001；！〕〜〔0158〕に記載にものが挙げられる。重合開始ポリマーの特に好ましいもの の具体例としては、以下に示すものが挙げられる。 001; ] To [0158]. Specific examples of particularly preferred polymerization initiating polymers include the following.

[0088] [化 7]

Figure imgf000026_0001
[0088] [Chemical 7]
Figure imgf000026_0001

Figure imgf000027_0001
重合開始層の成膜
Figure imgf000027_0001
Formation of polymerization initiation layer

本発明における重合開始ポリマーを用いてなる重合開始層は、上述の重合開始ポ リマーを適当な溶剤に溶解し、塗布液を調製し、その塗布液を基材上に塗布などに より配置し、溶剤を除去し、架橋反応が進行することにより成膜する。つまり、この架 橋反応が進行することにより、重合開始ポリマーが固定化される。この架橋反応によ る固定化には、重合開始ポリマーの自己縮合反応を使用する方法、及び架橋剤を併 用する方法があり、架橋剤を用いることが好ましい。重合開始ポリマーの自己縮合反 応を使用する方法の例としては、架橋性基が NCOである場合、熱をかけることに より自己縮合反応が進行する性質を利用する方法が挙げられる。この自己縮合反応 が進行することにより、架橋構造を形成することができる。 The polymerization initiating layer using the polymerization initiating polymer in the present invention is prepared by dissolving the above-mentioned polymerization initiating polymer in an appropriate solvent, preparing a coating solution, and arranging the coating solution on a substrate by coating or the like. The film is formed by removing the solvent and proceeding with the crosslinking reaction. In other words, the polymerization initiating polymer is immobilized as the bridge reaction proceeds. The immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a polymerization initiating polymer and a method using a crosslinking agent together, and it is preferable to use a crosslinking agent. Self-condensation reaction of polymerization initiator polymer As an example of the method using the reaction, when the crosslinkable group is NCO, there is a method using the property that the self-condensation reaction proceeds by applying heat. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

[0091] また、架橋剤を併用する方法に用いられる架橋剤としては、山下信二編「架橋剤ハ ンドブック」に掲載されているような従来公知のものを用いることができる。 [0091] As the crosslinking agent used in the method in which the crosslinking agent is used in combination, conventionally known crosslinking agents such as those described in Shinji Yamashita's “Crosslinking agent handbook” can be used.

重合開始ポリマー中の架橋性基と架橋剤との好ましい組み合わせとしては、（架橋 性基，架橋剤） = ( COOH,多価ァミン）、 (-COOH,多価アジリジン）、 (-COO H,多価イソシァネート）、 (-COOH,多価エポキシ）、 (-NH ,多価イソシァネート  Preferred combinations of a crosslinkable group and a crosslinker in the polymerization initiating polymer include (crosslinkable group, crosslinker) = (COOH, polyvalent amine), (-COOH, polyvalent aziridine), (-COO H, multiple -Valent isocyanate), (-COOH, polyvalent epoxy), (-NH2, polyvalent isocyanate)

2  2

)、 (-NH , アルデヒド類）、 (-NCO,多価ァミン）、 (-NCO,多価イソシァネート）  ), (-NH, aldehydes), (-NCO, polyvalent amine), (-NCO, polyvalent isocyanate)

2  2

、 (-NCO,多価アルコール）、 (-NCO,多価エポキシ）、 (-OH,多価アルコー ル）、 (-OH,多価ハロゲン化化合物）、 (-OH,多価ァミン）、 (-OH,酸無水物） 力 S挙げられる。中でも、架橋の後にウレタン結合が生成し、高い強度の架橋が形成可 能であるという点で、（官能基，架橋剤） = ( OH,多価イソシァネート）力 更に好ま しい組み合わせである。  , (-NCO, polyhydric alcohol), (-NCO, polyhydric epoxy), (-OH, polyhydric alcohol), (-OH, polyhydric halogenated compound), (-OH, polyhydric amine), ( -OH, acid anhydride) Force S Among them, (functional group, cross-linking agent) = (OH, polyvalent isocyanate) force is a more preferable combination in that a urethane bond is formed after cross-linking and a high-strength cross-linking can be formed.

[0092] 本発明における架橋剤の具体例としては、以下に示す構造のものが挙げられる。  [0092] Specific examples of the crosslinking agent in the present invention include those having the following structures.

[0093] [化 9]

Figure imgf000028_0001
Figure imgf000028_0002
[0093] [Chemical 9]
Figure imgf000028_0001
Figure imgf000028_0002

Figure imgf000028_0003
Figure imgf000028_0003

[0094] このような架橋剤は、重合開始層の成膜の際、上述の重合開始ポリマーを含有する 塗布液に添加される。その後、塗膜の加熱乾燥時の熱により、架橋反応が進行し、 強固な架橋構造を形成することができる。より詳細には、下記の exl.で示される脱 水反応や ex2.で示される付加反応により架橋反応が進行し、架橋構造が形成され る。これらの反応における温度条件としては、 50°C以上 300°C以下が好ましぐ更に 好ましくは 80°C以上 200°C以下である。 [0094] Such a crosslinking agent is added to the coating solution containing the above-mentioned polymerization initiating polymer when the polymerization initiating layer is formed. After that, the crosslinking reaction proceeds by the heat at the time of drying the coating film, A strong cross-linked structure can be formed. More specifically, a crosslinking reaction proceeds by a dehydration reaction shown by exl. Below or an addition reaction shown by ex2. A crosslinked structure is formed. The temperature condition in these reactions is preferably 50 ° C or higher and 300 ° C or lower, more preferably 80 ° C or higher and 200 ° C or lower.

[化 10] e x l . —OH + 一 OH → 0-  [Chemical 10] e x l. —OH + one OH → 0-

0 0

— COOH + — NH2 tl — COOH + — NH 2 tl

ひ

Figure imgf000029_0001
Hi
Figure imgf000029_0001

-NCO + -NH,  -NCO + -NH,

N HN H

N HN H

N H N H

[0096] また、塗布液中の架橋剤の添加量としては、重合開始ポリマー中に導入されている 架橋性基の量により変化するが、架橋度合や、未反応の架橋成分の残留による重合 反応への影響の観点から、通常、架橋性基のモル数に対して 0. 0；!〜 50当量である こと力好ましく、 0. 01〜； 10当量であることがより好ましぐ 0. 5〜3当量であることが 更に好ましい。  [0096] The addition amount of the crosslinking agent in the coating solution varies depending on the amount of the crosslinkable group introduced into the polymerization initiating polymer. However, the degree of crosslinking and the polymerization reaction due to residual unreacted crosslinking components remain. From the viewpoint of the influence on the number of moles, it is usually preferable that the amount is 0.0;! To 50 equivalents relative to the number of moles of the crosslinkable group, and that 0.01 to 10 equivalents is more preferable. More preferably, it is ˜3 equivalents.

[0097] また、重合開始層を塗布する際に用いる溶媒は、上述の重合開始ポリマーが溶解 するものであれば特に制限されない。乾燥の容易性、作業性の観点からは、沸点が 高すぎない溶媒が好ましぐ具体的には、沸点 40°C〜150°C程度のものを選択すれ ばよい。  [0097] The solvent used for applying the polymerization initiating layer is not particularly limited as long as the above-mentioned polymerization initiating polymer can be dissolved. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferred. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.

具体的には、アセトン、メチルェチルケトン、シクロへキサン、酢酸ェチル、テトラヒド 口フラン、トノレエン、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノ ェチノレエーテノレ、エチレングリコーノレジメチノレエーテノレ、プロピレングリコーノレモノメ チルエーテル、プロピレングリコールモノェチルエーテル、ァセチルアセトン、シクロ へキサノン、メタノール、エタノール、 1ーメトキシー2—プロパノール、 3—メトキシプロ ノ ノ一ノレ、ジエチレング!;コーノレモノメチノレエーテノレ、ジエチレング！;コーノレモノェチ ノレエーテノレ、ジエチレングリコーノレジメチノレエーテノレ、ジエチレングリコーノレジェチノレ エーテノレ、プロピレングリコーノレモノメチノレエーテノレアセテート、プロピレングリコーノレ モノェチルエーテルアセテート、 3—メトキシプロピルアセテートなどが挙げられる。 これらの溶媒は、単独或いは混合して使用することができる。そして塗布溶液中の 固形分の濃度は、 2〜50質量％が適当である。 Specific examples include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, tonoleene, ethylene glycol monomethino ethenore, ethylene glycol monomethino ethenore, ethylene glyconoresin methino rea. Tenole, Propylene glycol monomethyl ether, Propylene glycol monoethyl ether, Acetyl acetone, Cyclohexanone, Methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypro Nono Nore, Diethylenegu !; Conole Monomethino Rete Tenole, Diethylenegu! Cornole monoethylenoate, diethylene glyconoresin methinore etherenore, diethylene glycono lesino ethenore, propylene glycoleno monomethino ethenore acetate, propylene glycol monoleethyl ether acetate, 3-methoxypropyl acetate and the like. These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

[0098] 重合開始ポリマーを用いてなる重合開始層の塗布量は、表面グラフト重合の開始 能や、膜性の観点から、乾燥後の質量で、 0. ；!〜 20g/m2が好ましぐ更に、；!〜 15 g/m2が好ましい。 [0098] The coating amount of the polymerization initiating layer using the polymerization initiating polymer is preferably from 0.;! To 20 g / m 2 in terms of the mass after drying from the viewpoint of the ability to initiate surface graft polymerization and film properties. More preferably, !!-15 g / m 2 is preferred.

[0099] 更に、本発明において、前述のような、絶縁性樹脂からなる層を基材上に有する基 板を用いる場合、この絶縁性樹脂からなる層中に、公知の重合開始剤を含有させて 、絶縁性の重合開始層とすることが好ましい。この絶縁性の重合開始層中に含有さ せる重合開始剤としては、特に制限はなぐ例えば、前述の、熱重合開始剤、光重合 開始剤 (ラジカル重合開始剤、ァユオン重合開始剤、カチオン重合開始剤)や、特開 平 9 77891号、特開平 10— 45927号に記載の活性カルボ二ル基を側鎖に有する 高分子化合物、更には、側鎖に重合開始能を有する官能基及び架橋性基を有する ポリマー（重合開始ポリマー）などを用いることができる。  [0099] Further, in the present invention, when a substrate having a layer made of an insulating resin as described above is used, a known polymerization initiator is contained in the layer made of the insulating resin. Thus, an insulating polymerization initiating layer is preferable. The polymerization initiator contained in the insulating polymerization initiator layer is not particularly limited.For example, the above-described thermal polymerization initiator, photopolymerization initiator (radical polymerization initiator, cation polymerization initiator, cationic polymerization initiator). Agent), a polymer compound having an active carbonyl group described in JP-A-9 77891 and JP-A-10-45927 in the side chain, and further, a functional group having a polymerization initiating ability in the side chain and a crosslinking property A polymer having a group (polymerization initiating polymer) or the like can be used.

絶縁性の重合開始層中に含有させる重合開始剤の量は、一般的には、絶縁層中 に固形分で 0. ；!〜 50質量％程度であることが好ましぐ 1. 0-30. 0質量％程度で あることがより好ましい。  In general, the amount of the polymerization initiator contained in the insulating polymerization initiating layer is preferably about 0.;! To 50% by mass in terms of solid content in the insulating layer. 1. 0-30 More preferably, it is about 0% by mass.

[0100] グラフトポリマーの生成  [0100] Formation of graft polymer

(al)工程におけるグラフトポリマーの生成態様としては、前述した如ぐ基板表面に 存在する官能基と、高分子化合物がその末端又は側鎖に有する反応性官能基との カップリング反応を利用する方法や、光グラフト重合法を用いることができる。  In the step (al), the graft polymer is generated by using a coupling reaction between the functional group present on the substrate surface as described above and the reactive functional group of the polymer compound at its terminal or side chain. Alternatively, a photograft polymerization method can be used.

本発明においては、基材上に重合開始層が形成された基板を用い、該重合開始 層上に、めっき触媒又はその前駆体と相互作用を形成する官能基 (相互作用性基） を有し、且つ、該重合開始層と直接化学結合したポリマーからなるポリマー層を形成 する態様〔(al— 2)工程〕が好ましい。更に好ましくは、重合開始層上に、重合性基 及び相互作用性基を有するポリマーを接触させた後、エネルギーを付与することによ り、前記基板表面全体 (重合開始層表面全体）に当該ポリマーを直接化学結合させ る態様である。即ち、重合性基及び相互作用性基を有する化合物を含有する組成物 を、重合開始層表面に接触させながら、当該重合開始層表面に生成する活性種に より直接結合させるものである。 In the present invention, a substrate having a polymerization initiating layer formed on a substrate is used, and the polymerization initiating layer has a functional group (interactive group) that forms an interaction with the plating catalyst or its precursor. In addition, an embodiment in which a polymer layer composed of a polymer directly chemically bonded to the polymerization initiation layer [(al-2) step] is preferable. More preferably, a polymerizable group is formed on the polymerization initiating layer. In addition, after the polymer having an interactive group is brought into contact, energy is applied to the polymer to directly chemically bond the polymer to the entire substrate surface (the entire polymerization initiation layer surface). That is, a composition containing a compound having a polymerizable group and an interactive group is directly bonded to the surface of the polymerization initiation layer while being brought into contact with the active species generated on the surface of the polymerization initiation layer.

[0101] 上記接触は、重合開始層が形成された基板を、重合性基及び相互作用性基を有 する化合物を含有する液状の組成物（本発明のポリマー層形成用組成物）中に浸漬 することで行ってもよいが、取り扱い性や製造効率の観点からは、後述するように、重 合性基及び相互作用性基を有する化合物を含有する組成物（本発明のポリマー層 形成用組成物）からなる層を基板表面（重合開始層表面）に、塗布法により形成する ことが好ましい。 [0101] In the above contact, the substrate on which the polymerization initiating layer is formed is immersed in a liquid composition containing the compound having a polymerizable group and an interactive group (the composition for forming a polymer layer of the present invention). However, from the viewpoint of handleability and production efficiency, as described later, a composition containing a compound having a polymerizable group and an interactive group (the composition for forming a polymer layer of the present invention). It is preferable to form a layer composed of a product on the substrate surface (polymerization initiation layer surface) by a coating method.

なお、本発明の第 3の表面金属膜材料の作製方法における（al")工程のように、 樹脂フィルムの両面に対してポリマー層を形成する場合にも、ポリマー層を両面同時 に形成し易いとレ、つた観点から、塗布法を用いることが好まし!/、。  Even when the polymer layer is formed on both sides of the resin film as in the (al ") step in the third method for producing the surface metal film material of the present invention, it is easy to form the polymer layer on both sides simultaneously. From the point of view, it is preferable to use a coating method!

[0102] 本発明において、表面グラフト重合法により、グラフトポリマーを生成させる場合に 用いられる、重合性基及び相互作用性基を有する化合物について説明する。 [0102] In the present invention, a compound having a polymerizable group and an interactive group, which is used when a graft polymer is formed by a surface graft polymerization method, will be described.

本発明における重合性基及び相互作用性基を有する化合物としては、生成したグ ラフトポリマーからなるポリマー層が、前記;!〜 4の条件を全て満たすように、重合性 基及び相互作用性基を有すると共に、吸水性が低ぐ更に、疎水性の高い化合物を 用いることが好ましい。  The compound having a polymerizable group and an interactive group in the present invention includes a polymerizable group and an interactive group so that the polymer layer formed of the generated graph polymer satisfies all the conditions of! In addition, it is preferable to use a compound having low water absorption and high hydrophobicity.

この化合物における相互作用性基としては非解離性官能基であることが好ましぐ 非解離性官能基とは、官能基が解離によりプロトンを生成しない官能基を意味する。 このような官能基は、めっき触媒又はその前駆体と相互作用を形成する機能はあつ ても、解離性の極性基 (親水性基）のように高い吸水性、親水性を有するものではな いため、この官能基を有するグラフトポリマーからなるポリマー層は、前記;!〜 4の条 件を満たすことが可能になる。  The interactive group in this compound is preferably a non-dissociable functional group. The non-dissociable functional group means a functional group that does not generate a proton upon dissociation. Such a functional group has a function of forming an interaction with the plating catalyst or its precursor, but does not have high water absorption and hydrophilicity unlike a dissociative polar group (hydrophilic group). In addition, the polymer layer composed of the graft polymer having this functional group can satisfy the above-mentioned conditions!

[0103] 本発明における重合性基は、エネルギー付与により、重合性基及び相互作用性基 を有する化合物同士、又は、重合性基及び相互作用性基を有する化合物と基板とが 結合する官能基であり、具体的には、ビュル基、ビュルォキシ基、ァリル基、アタリ口 ィル基、メタクリロイル基、ォキセタン基、エポキシ基、イソシァネート基、活性水素を 含む官能基、ァゾ化合物における活性基などが挙げられる。 [0103] The polymerizable group in the present invention is a compound between a compound having a polymerizable group and an interactive group, or a compound having a polymerizable group and an interactive group and a substrate by energy application. Specifically, it is a functional group that binds, specifically in a bur group, a buroxy group, an allyl group, an attalyl group, a methacryloyl group, an oxetane group, an epoxy group, an isocyanate group, a functional group containing an active hydrogen, or an azo compound. An active group etc. are mentioned.

[0104] 本発明における相互作用性基としては、具体的には、金属イオンと配位形成可能 な基、含窒素官能基、含硫黄官能基、含酸素官能基などが好ましぐ具体的には、ィ ミド基、ピリジン基、 3級のアミノ基、アンモニゥム基、ピロリドン基、アミジノ基、トリアジ ン環構造を含む基、イソシァヌル構造を含む基、ニトロ基、ニトロソ基、ァゾ基、ジァゾ 基、アジド基、シァノ基、シァネート基 (R— O CN)などの含窒素官能基、エーテル 基、カルボニル基、エステル基、 N ォキシド構造を含む基、 S ォキシド構造を含 む基、 N ヒドロキシ構造を含む基などの含酸素官能基、チォエーテル基、チォキシ 基、スルホキシド基、スルホン基、サルファイト基、スルホキシィミン構造を含む基、ス ルホキシュゥム塩構造を含む基、スルホン酸エステル構造を含む基などの含硫黄官 能基、フォスフィン基などの含リン官能基、塩素、臭素などのハロゲン原子を含む基、 及び不飽和エチレン基等が挙げられる。また、隣接する原子又は原子団との関係に より非解離性を示す態様であれば、イミダゾール基、ウレァ基、チォゥレア基を用いて あよい。 [0104] As the interactive group in the present invention, specifically, a group capable of forming a coordination with a metal ion, a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group and the like are preferable. Is an imido group, a pyridine group, a tertiary amino group, an ammonium group, a pyrrolidone group, an amidino group, a group containing a triazine ring structure, a group containing an isocyanuric structure, a nitro group, a nitroso group, an azo group or a diazo group. Nitrogen-containing functional groups such as azide group, cyano group, cyanate group (R—OCN), ether group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, N-hydroxy structure Oxygen-containing functional groups such as thioether groups, thioether groups, thioxyl groups, sulfoxide groups, sulfone groups, sulfite groups, groups containing sulfoxymine structures, groups containing sulfoxum salt structures, sulfonic acid esters Sulfur-containing officers functional group such as a group containing a structure, phosphorus-containing functional groups, such as phosphine group, chlorine, a group containing a halogen atom such as bromine, and unsaturated ethylenic group and the like. In addition, an imidazole group, a urea group, or a thiourea group may be used as long as it is non-dissociative due to the relationship with an adjacent atom or atomic group.

中でも、極性が高ぐめっき触媒等への吸着能が高いことから、エーテル基はり具 体的には、 O （CH ) O （nは 1〜5の整数)で表される構造）、又はシァノ基  Above all, because of its high adsorption ability to highly polar plating catalysts, the ether group specifically has a structure represented by O (CH) O (where n is an integer of 1 to 5), or cyan Base

2 n  2 n

が特に好ましぐシァノ基が最も好ましいものとして挙げられる。  A particularly preferred cyano group is mentioned as the most preferred one.

[0105] 一般的に、高極性になるほど吸水率が高くなる傾向である力 シァノ基はポリマー 層中にて互いに極性を打ち消しあうように相互作用しあうため、膜が緻密になり、且 つ、ポリマー層全体としての極性が下がるため、吸水性が低くなる。また、後述する（a 2)工程において、ポリマー層の良溶剤にて触媒を吸着させることで、シァノ基が溶媒 和されてシァノ基間の相互作用がなくなり、めっき触媒と相互作用できるようになる。 以上のことから、シァノ基を有するポリマー層は低吸湿でありながら、めっき触媒とは よく相互作用をする、相反する性能を発揮する点で、好ましい。 [0105] In general, the force that tends to increase the water absorption as the polarity becomes higher. The cyan groups interact in the polymer layer so as to cancel each other's polarity, so that the film becomes dense and Since the polarity of the entire polymer layer is lowered, the water absorption is lowered. In addition, in the step (a2) described later, by adsorbing the catalyst with a good solvent in the polymer layer, the cyano group is solvated and the interaction between the cyano groups is eliminated, and the interaction with the plating catalyst can be achieved. . In view of the above, a polymer layer having a cyano group is preferred in that it exhibits low performance while exhibiting contradictory performance that interacts well with the plating catalyst.

また、本発明における相互作用性基としては、アルキルシアノ基であることが更に好 ましい。これは、芳香族シァノ基は芳香環に電子を吸引されており、めっき触媒等へ の吸着性として重要な不対電子の供与性が低めになるが、アルキルシアノ基はこの 芳香環が結合してレ、なレ、ため、めっき触媒等への吸着性の点で好まし!/、。 Further, the interactive group in the present invention is more preferably an alkyl cyano group. This is because the aromatic cyano group attracts electrons to the aromatic ring, leading to a plating catalyst, etc. Although the donating property of unpaired electrons, which is important as the adsorptive property of the metal, is low, the alkyl cyano group is preferred because of its adsorptive properties to the plating catalyst, etc. ,.

[0106] 本発明において、重合性基及び相互作用性基を有する化合物は、モノマー、マク 口モノマー、ポリマーのいずれの形態あってもよぐ中でも、ポリマー層の形成性と、制 御の容易性の観点から、ポリマー（重合性基及び相互作用性基を有するポリマー）を 用いることが好ましい。 [0106] In the present invention, the compound having a polymerizable group and an interactive group may be in any form of a monomer, a macromonomer, and a polymer, and the formability of the polymer layer and the ease of control. From this point of view, it is preferable to use a polymer (a polymer having a polymerizable group and an interactive group).

重合性基及び相互作用性基を有するポリマーとしては、相互作用性基を有するモ ノマーを用いて得られるホモポリマーゃコポリマーに、重合性基として、ビュル基、ァ リル基、（メタ）アクリル基などのエチレン付加重合性不飽和基（重合性基）を導入した ポリマーであることが好ましぐこの重合性基及び相互作用性基を有するポリマーは、 少なくとも主鎖末端又は側鎖に重合性基を有するものであり、側鎖に重合性基を有 するものが好ましい。  As the polymer having a polymerizable group and an interactive group, a homopolymer copolymer obtained by using a monomer having an interactive group is used, and a polymerizable group includes a bur group, an aryl group, and a (meth) acryl group. Polymers having this polymerizable group and interacting group, which are preferably polymers having an ethylenically-added polymerizable unsaturated group (polymerizable group) introduced, such as a polymerizable group at least at the end or side chain of the main chain Those having a polymerizable group in the side chain are preferred.

[0107] 前記重合性基及び相互作用性基を有するポリマーを得る際に用いられる相互作用 性基を有するモノマーとしては、前記記載の非解離性官能基を有するモノマーであ ればいかなるモノマーも使用可能であるが、例えば、具体的には、以下に示すものが 挙げられる。  [0107] As the monomer having an interactive group used in obtaining the polymer having a polymerizable group and an interactive group, any monomer may be used as long as it is a monomer having the non-dissociative functional group described above. Although it is possible, specific examples include the following.

これらは 1種を単独で使用してもよい、 2種以上を併用してもよい。  These may be used alone or in combination of two or more.

[0108] [化 11] [0108] [Chemical 11]

Figure imgf000034_0001
Figure imgf000034_0001

[0109] [化 12] [0109] [Chemical 12]

CN CN

\广¾へ  To \ 广 ¾

ο b レ〜  ο b

Figure imgf000035_0001
Figure imgf000035_0001

[0110] 重合性基及び相互作用性基を有するポリマーにおいて、相互作用性基を有するモ ノマーに由来するユニットは、めっき触媒又はその前駆体との相互作用形成性の観 点から、重合性基及び相互作用性基を有するポリマー中に、 50〜95モル％の範囲 で含有されること力好ましく、 40〜80モル％の範囲で含有されることがより好ましい。 [0110] In the polymer having a polymerizable group and an interactive group, the unit derived from the monomer having the interactive group is a polymerizable group from the viewpoint of interaction formation with the plating catalyst or its precursor. In the polymer having an interactive group, it is preferably contained in the range of 50 to 95 mol%, more preferably in the range of 40 to 80 mol%.

[0111] また、重合性基及び相互作用性基を有するポリマーを得る際には、吸水性を低下 させるため、また、疎水性を向上させるために、上記相互作用性基を有するモノマー 以外に他のモノマーを用いてもよい。他のモノマーとしては、一般的な重合性モノマ 一を用いてよぐジェン系モノマー、アクリル系モノマー等が挙げられる。中でも、無 置換アルキルのアクリル系モノマーが好ましい。具体的には、ターシャリーブチルァク リレート、 2—ェチルへキシルアタリレート、ブチルアタリレート、シクロへキシルアタリレ ート、ベンジルメタタリレートなどが好ましく使用できる。 [0111] In addition, when obtaining a polymer having a polymerizable group and an interactive group, in addition to the above-mentioned monomer having an interactive group, in order to reduce water absorption and improve hydrophobicity. These monomers may be used. Examples of the other monomer include a gen-based monomer and an acrylic monomer using a general polymerizable monomer. Of these, unsubstituted alkyl acrylic monomers are preferred. Specifically, tertiary butyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, cyclohexyl acrylate. And benzyl methacrylate are preferably used.

[0112] このような重合性基及び相互作用性基を有するポリマーは、以下のように合成でき 合成方法としては、 i)相互作用性基を有するモノマーと重合性基を有するモノマー とを共重合する方法、 ii)相互作用性基を有するモノマーと二重結合前駆体を有する モノマーとを共重合させ、次に塩基などの処理により二重結合を導入する方法、 iii) 相互作用性基を有するポリマーと重合性基を有するモノマーとを反応させ、二重結 合を導入 (重合性基を導入する）方法が挙げられる。好ましいのは、合成適性の観点 から、 ii)相互作用性基を有するモノマーと二重結合前駆体を有するモノマーとを共 重合させ、次に塩基などの処理により二重結合を導入する方法、 iii)相互作用性基を 有するポリマーと重合性基を有するモノマーとを反応させ、重合性基を導入する方法 である。 [0112] Such a polymer having a polymerizable group and an interactive group can be synthesized as follows. As a synthesis method, i) a monomer having an interactive group and a monomer having a polymerizable group are copolymerized. Ii) a method in which a monomer having an interactive group and a monomer having a double bond precursor are copolymerized and then introducing a double bond by treatment with a base or the like, iii) having an interactive group There is a method of introducing a double bond (introducing a polymerizable group) by reacting a polymer and a monomer having a polymerizable group. From the viewpoint of synthesis suitability, ii) a method in which a monomer having an interactive group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like, iii ) A method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.

[0113] 重合性基及び相互作用性基を有するポリマーの合成に用いられる、相互作用性基 を有するモノマーとしては、上記の相互作用性基を有するモノマーと同様のモノマー を用いること力 Sできる。モノマーは、一種単独で用いてもよいし、 2種以上を併用して あよい。  [0113] As a monomer having an interactive group used for the synthesis of a polymer having a polymerizable group and an interactive group, it is possible to use the same monomer as the monomer having an interactive group. Monomers may be used alone or in combination of two or more.

[0114] 相互作用性基を有するモノマーと共重合させる重合性基を有するモノマーとしては 、ァリル (メタ）アタリレート、 2—ァリルォキシェチルメタタリレートなどが挙げられる。 また、二重結合前駆体を有するモノマーとしては 2—（3 クロロー 1 ォキソプロボ キシ）ェチルメタクリレー卜、 2 （3—ブロモー 1 ォキソプロポキシ）ェチルメタクリレ ート、などが挙げられる。  [0114] Examples of the monomer having a polymerizable group to be copolymerized with the monomer having an interactive group include allyl (meth) acrylate and 2-aryloxetyl methacrylate. Examples of the monomer having a double bond precursor include 2- (3 chloro-1-oxopropoxy) ethyl methacrylate, 2 (3-bromo-1-oxopropoxy) ethyl methacrylate, and the like.

[0115] 更に、相互作用性基を有するポリマー中の、カルボキシル基、アミノ基若しくはそれ らの塩、水酸基、及びエポキシ基などの官能基との反応を利用して不飽和基を導入 するために用いられる重合性基を有するモノマーとしては、（メタ）アクリル酸、グリシ ジル（メタ）アタリレート、ァリルグリシジルエーテル、 2—イソシアナトェチル（メタ）ァク リレートなどがある。  [0115] Furthermore, in order to introduce an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in a polymer having an interactive group. Examples of the monomer having a polymerizable group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

[0116] 以下、本発明において好適に用いられる重合性基及び相互作用性基を有するポリ マーの具体例を示す力 S、本発明はこれに限定されるものではない。 [0117] [化 13] [0116] Hereinafter, the force S indicating a specific example of a polymer having a polymerizable group and an interactive group that is preferably used in the present invention, the present invention is not limited thereto. [0117] [Chemical 13]

Figure imgf000037_0001
Figure imgf000037_0001

[0118] [化 14]

Figure imgf000038_0001
[0118] [Chemical 14]
Figure imgf000038_0001

0入。 X^NH：、 ζ 、γ 0 in. X ^ NH :, ζ, γ

1 、 Ό 1, Ό

Figure imgf000038_0002
5]
Figure imgf000038_0002
Five]

Figure imgf000039_0001
Figure imgf000039_0001

Figure imgf000039_0002
Figure imgf000039_0002

[0120] 本発明の一態様である表面金属膜材料の作製方法において用いられる、重合性 基及び相互作用性基を有するポリマーとしては、相互作用性基としてシァノ基を有す るポリマー（以下、「シァノ基含有重合性ポリマー」と称する。）が好ましい。 [0120] As the polymer having a polymerizable group and an interactive group used in the method for producing a surface metal film material which is one embodiment of the present invention, a polymer having a cyano group as an interactive group (hereinafter referred to as "interactive group"). (Referred to as “cyan group-containing polymerizable polymer”).

[0121] 本発明におけるシァノ基含有重合性ポリマー等の重合性基及び相互作用性基を 有する化合物は、重合性基と相互作用性基の他に、極性基を有していてもよい。 特に、本発明に従う表面金属膜材料を作製する場合には、形成されたポリマー層 が前記 1〜4の条件の全てを満たす範囲であれば、該ポリマーが極性基を有している ことによって、後述の工程により金属膜が形成された後、例えば、保護層を設ける場 合には、ポリマー層と保護層との接触領域において密着力を向上させることができる [0121] The compound having a polymerizable group and an interactive group such as a cyano group-containing polymerizable polymer in the present invention may have a polar group in addition to the polymerizable group and the interactive group. In particular, when producing a surface metal film material according to the present invention, if the formed polymer layer satisfies the above conditions 1 to 4, the polymer has a polar group. After the metal film is formed by a process described later, for example, when a protective layer is provided, the adhesion can be improved in the contact region between the polymer layer and the protective layer.

〇 Yes

[0122] 前述のように、本発明におけるポリマー層を形成するためには、重合性基及び相互 作用性基を有するポリマー等の重合性基及び相互作用性基を有する化合物を含有 する液状組成物、即ち、重合性基及び相互作用性基を有する化合物と、該化合物を 溶解しうる溶剤と、を含有する組成物（好ましくは、シァノ基又は O （CH ) O  [0122] As described above, in order to form the polymer layer in the present invention, a liquid composition containing a compound having a polymerizable group and an interactive group such as a polymer having a polymerizable group and an interactive group. That is, a composition containing a compound having a polymerizable group and an interactive group and a solvent capable of dissolving the compound (preferably a cyan group or O (CH) O

2 n 一（nは 1〜5の整数)で表される構造、及び重合性基を有するポリマーと、該ポリマー を溶解しうる溶剤と、を含有する本発明のポリマー層形成用組成物）を用いることが 好ましい。 2 n one (where n is an integer of 1 to 5), a polymer having a polymerizable group, and the polymer It is preferable to use a polymer layer forming composition of the present invention containing a solvent capable of dissolving

なお、重合性基及び相互作用性基を有する化合物 (例えば、シァノ基含有重合性 ポリマー）の組成物中の含有量は、組成物全体に対して、 2質量％〜50質量％であ ることが好ましい。  The content of the compound having a polymerizable group and an interactive group (for example, a cyano group-containing polymerizable polymer) in the composition is 2% by mass to 50% by mass with respect to the entire composition. Is preferred.

[0123] 上記組成物に使用する溶剤は、組成物の主成分である、重合性基及び相互作用 性基を有する化合物が溶解可能ならば特に制限はない。溶剤には、更に界面活性 剤を添加してもよい。  [0123] The solvent used in the composition is not particularly limited as long as the compound having a polymerizable group and an interactive group, which is a main component of the composition, can be dissolved. A surfactant may be further added to the solvent.

使用できる溶剤としては、例えば、メタノール、エタノール、プロパノール、エチレン グリコーノレ、グリセリン、プロピレングリコーノレモノメチノレエーテノレの如きァノレコーノレ系 溶剤、酢酸の如き酸、アセトン、メチルェチルケトン、シクロへキサノンの如きケトン系 溶剤、ホノレムアミド、ジメチルァセトアミド、 N—メチルピロリドンの如きアミド系溶剤、ァ セトニトリル、プロピロ二トリルの如き二トリル系溶剤、酢酸メチル、酢酸ェチルの如き エステル系溶剤、ジメチルカーボネート、ジェチルカーボネートの如きカーボネート系 溶剤などが挙げられる。  Solvents that can be used include, for example, methanolic solvents such as methanol, ethanol, propanol, ethylene glycolenole, glycerin, propylene glycolenomonomethylenoateolate, acids such as acetic acid, acetone, methyl ethyl ketone, and cyclohexanone. Ketone solvents, honolemamide, dimethylacetamide, amide solvents such as N-methylpyrrolidone, nitrile solvents such as acetonitrile and propylnitrile, ester solvents such as methyl acetate and ethyl acetate, dimethyl carbonate, jetyl And carbonate-based solvents such as carbonate.

この中でも、シァノ基含有重合性ポリマーを用いた組成物とする場合には、アミド系 、ケトン系、二トリル系溶剤、カーボネート系溶剤が好ましぐ具体的には、アセトン、 ジメチルァセトアミド、メチルェチルケトン、シクロへキサノン、ァセトニトリル、プロピオ 二トリル、 N—メチルピロリドン、ジメチルカーボネートが好ましい。  Among these, in the case of a composition using a cyano group-containing polymerizable polymer, amide type, ketone type, nitrile type solvent, carbonate type solvent are preferred, specifically acetone, dimethylacetamide, Methyl ethyl ketone, cyclohexanone, acetonitrile, propionitryl, N-methylpyrrolidone and dimethyl carbonate are preferred.

また、シァノ基含有重合性ポリマーを含有する組成物を塗布する場合は、取り扱い 安さから沸点が 50〜； 150°Cの溶剤が好ましい。なお、これらの溶剤は単一で使用し てもよいし、混合して使用してもよい。  In addition, when a composition containing a cyano group-containing polymerizable polymer is applied, a solvent having a boiling point of 50 to 150 ° C. is preferable from the viewpoint of ease of handling. These solvents may be used alone or in combination.

[0124] また、本発明にお!/、て、重合性基及び相互作用性基を有する化合物を含有する組 成物を、基板や重合開始層上に塗布する場合、基板や重合開始層の吸溶媒率が 5 〜25%となる溶剤を選択することができる。この吸溶媒率は、基板や、重合開始層を 形成した基材を溶剤中に浸漬し、 1000分後に引き上げた場合の質量の変化から求 めること力 Sでさる。 [0124] Further, in the present invention, when a composition containing a compound having a polymerizable group and an interactive group is applied onto a substrate or a polymerization initiation layer, the substrate or the polymerization initiation layer is coated. A solvent having a solvent absorption of 5 to 25% can be selected. This solvent absorption is determined by the force S obtained from the change in mass when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in the solvent and pulled up after 1000 minutes.

また、重合性基及び相互作用性基を有する化合物を含有する組成物を、基板や重 合開始層上に塗布する場合、基板や重合開始層の膨潤率が 10〜45%となる溶剤 を選択してもよい。この膨潤率は、基板や、重合開始層を形成した基材を溶剤中に 浸漬し、 1000分後に引き上げた場合の厚さの変化から求めることができる。 In addition, a composition containing a compound having a polymerizable group and an interactive group is added to a substrate or a substrate. In the case of coating on the combined initiation layer, a solvent in which the swelling ratio of the substrate or the polymerization initiation layer is 10 to 45% may be selected. This swelling ratio can be determined from the change in thickness when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in a solvent and pulled up after 1000 minutes.

[0125] 必要に応じて溶剤に添加することのできる界面活性剤は、溶剤に溶解するものであ ればよぐそのような界面活性剤としては、例えば、 n—ドデシルベンゼンスルホン酸 ナトリウムの如きァニオン性界面活性剤や、 n—ドデシルトリメチルアンモニゥムクロラ イドの如きカチオン性界面活性剤、ポリオキシエチレンノユルフェノールエーテル（巿 販品としては、例えば、ェマルゲン 910、花王 (株)製などが挙げられる）、ポリオキシ エチレンソルビタンモノラウレート（市販品としては、例えば、商品名「ツイーン 20」な どが挙げられる）、ポリオキシエチレンラウリルエーテルの如き非イオン性界面活性剤 等が挙げられる。 [0125] The surfactant that can be added to the solvent as needed is only required to be soluble in the solvent. Examples of such a surfactant include sodium n-dodecylbenzenesulfonate. Anionic surfactants, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nourol phenol ether (for example, Emulgen 910, manufactured by Kao Corporation) And polyoxyethylene sorbitan monolaurate (commercially available products include, for example, trade name “Tween 20”), and nonionic surfactants such as polyoxyethylene lauryl ether.

[0126] また、必要に応じて可塑剤を添加することもできる。使用できる可塑剤としては、一 般的な可塑剤が使用でき、フタル酸エステル類 (ジメチルエステル、ジェチルエステ ノレ、ジブチルエステル、ジー 2—ェチルへキシルエステル、ジノルマルォクチルエス テノレ、ジィソノニノレエステノレ、ジノニノレエステノレ、ジイソデシノレエステノレ、ブチノレべンジ ノレエステル）、アジピン酸エステル類（ジォクチルエステル、ジイソノニルエステノレ）、 ァゼラインサンジォクチル、セバシンサンエステル類（ジブチルエステル、ジォクチル エステル）リン酸トリクレシル、ァセチルクェン酸トリブチル、エポキシ化大豆油、トリメリ ット酸トリオクチル、塩素化パラフィンゃジメチルァセトアミド、 N—メチルピロリドンのよ うな高沸点溶媒も使用することができる。  [0126] A plasticizer may be added as necessary. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, jetyl ester, dibutyl ester, di-2-ethyl hexyl ester, dinormaroctyl ester, disononino ester. Nore, dinonino estenole, diisodecinole estenole, butinoleven dinole ester), adipic acid ester (dioctyl ester, diisononyl estenole), azelain san dioctyl, sebacin san ester (dibutyl ester, High boiling solvents such as dioctyl ester) tricresyl phosphate, tributyl acetyl citrate, epoxidized soybean oil, trioctyl trimellitate, chlorinated paraffin, dimethylacetamide, N-methylpyrrolidone can also be used.

[0127] 重合性基及び相互作用性基を有する化合物を含有する組成物には、必要に応じ て、重合禁止剤を添加することもできる。使用できる重合禁止剤としては、ハイドロキ ノン、ジターシャリーブチルハイドロキノン、 2, 5—ビス（1 , 1 , 3, 3—テトラメチルブチ ノレ）ハイドロキノンなどのハイドロキノン類、 p—メトキシフエノール、フエノールなどのフ ェノール類、ベンゾキノン類、 TEMPO (2, 2, 6, 6—テトラメチルー 1ーピペリジニロ キシ フリーラジカル）、 4ーヒドロキシ TEMPOなどのフリーラジカル類、フエノチアジ ン類、 N—ニトロソフエニルヒドロキシァミン、そのアルミニウム塩などのニトロソァミン類 、カテコール類を使用することができる。 また、重合性基及び相互作用性基を有する化合物を含有する組成物には、必要に 応じて、重合開始層の硬化を進めるために、硬化剤及び/又は硬化促進剤を添カロ すること力 Sできる。硬化剤及び硬化促進剤としては、公知のものを用いることができる 。具体的には、硬化促進剤として、重付加型では、脂肪族ポリアミン、脂環族ポリアミ ン、芳香族ポリアミン、ポリアミド、酸無水物、フエノール、フエノールノポラック、ポリメ ルカブタン、活性水素を 2個以上持つ化合物等、触媒型としては、脂肪族第三アミン 、芳香族第三アミン、イミダゾール化合物、ルイス酸錯体などが挙げられる。 [0127] A polymerization inhibitor may be added to the composition containing a compound having a polymerizable group and an interactive group, if necessary. Polymerization inhibitors that can be used include hydroquinones such as hydroquinone, ditertiary butyl hydroquinone and 2,5-bis (1,1,3,3-tetramethylbutynole) hydroquinone, and phenols such as p-methoxyphenol and phenol. Enols, benzoquinones, TEMPO (2, 2, 6, 6-tetramethyl-1-piperidinyloxy free radical), free radicals such as 4-hydroxy TEMPO, phenothiazines, N-nitrosophenylhydroxylamine, aluminum salts, etc. Nitrosamines and catechols can be used. In addition, the composition containing a compound having a polymerizable group and an interactive group can be added with a curing agent and / or a curing accelerator to advance the curing of the polymerization initiation layer, if necessary. S can. Known curing agents and curing accelerators can be used. Specifically, as a curing accelerator, polyaddition type aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyamides, acid anhydrides, phenols, phenol nopolacs, polymer kabutanes, active hydrogens, 2 or more Examples of the catalyst type, such as a compound having an aliphatic tertiary amine, an aromatic tertiary amine, an imidazole compound, and a Lewis acid complex.

また、熱、光、湿気、圧力、酸、塩基などにより硬化開始するものとしては、ジェチレ ントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジェチルァミノプロピル ァミン、ポリアミドアミン、メンセンジァミン、イソホロンジァミン、 N アミノエチノレビペラ ジン、 3, 9 ビス（3 ァミノプロピル）一 2, 4, 8, 10 テトラオキシスピロ（5, 5)ゥン デカンァダクト、ビス（4—ァミノ一 3—メチルシクロへキシル）メタン、ビス（4—アミノシ クロへキシノレ）メタン、 m—キシレンジァミン、ジアミノジフエニルメタン、 m—フエ二レン ジァミン、ジアミノジフエニルスルホン、ジシアンジアミド、アジピン酸ジヒラジド、無水フ タル酸、テトラヒドロ無水フタル酸、へキサヒドロ無水フタル酸、メチルテトラヒドロ無水 フタル酸、メチルへキサヒドロ無水フタル酸、無水メチルナジック酸、ドデシル無水コ ハク酸、無水クロレンディック酸、無水ピロメリット酸、ベンゾフエノンテトラカルボン酸 無水物、エチレングリコールビス（アンヒドロトリメート）、メチルシクロへキセンテトラ力 ルボン酸無水物、無水トリメリット酸、ポリアゼライン酸無水物、フエノールノポラック、 キシリレンノボラック、ビス Aノボラック、トリフエニルメタンノボラック、ビフエニルノボラッ ク、ジシクロペンタジェンフエノーノレノボラック、テノレペンフエノーノレノボラック、ポリメノレ カフ。タン、ポリサノレフアイド、 2, 4, 6 トリス（ジメチノレ ミノメチノレ）フエノーノレ、 2, 4, 6 -トリス（ジメチルアミノメチル）フエノール—トリ 2 ェチルへキシル酸塩、ベンジ ノレジメチルァミン、 2—(ジメチルアミノメチノレ）フエノール 2—メチルイミダゾール、 2— ェチルー 4ーメチルイミダゾール 2 ゥンデシルイミダゾール、 2 ヘプタデシルイミダ ゾール、 2—フエ二ルイミダゾール、 1一べンジルー 2—メチルイミダゾール、 1ーシァ ノエチルー 2 メチルイミダゾール、 2, 4 ジアミノー 6—（2 メチルイミダゾリルー（1 ) )—ェチル S トリァジン、 BFモノェチルアミン錯体、ノレイス酸錯体、有機酸ヒドラジ ド、ジァミノマレオニトリル、メラミン誘導体、イミダゾール誘導体、ポリアミン塩、ァミン イミド化合物、芳香族ジァゾニゥム塩、ジァリルョードニゥム塩、トリアリルスルホニゥム 塩、トリァリルセレニウム塩、ケチミン化合物などが挙げられる。 In addition, those that begin to cure by heat, light, moisture, pressure, acid, base, etc. include: ethylene triamine, triethylenetetramine, tetraethylenepentamine, jetylaminopropylamine, polyamidoamine, mensendiamine, isophoronediamine. N-aminoethinoleviprazine, 3,9 bis (3aminopropyl) -1,2,4,8,10 tetraoxyspiro (5,5) undecandduct, bis (4-amino-1-methylcyclohexyl) methane, Bis (4-aminocyclohexenole) methane, m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro Phthalic anhydride, methyltetrahydro phthalic anhydride , Methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), methylcyclo Hexene tetra force Rubonic acid anhydride, trimellitic anhydride, polyazeline acid anhydride, phenol nopolac, xylylene novolac, bis A novolac, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol enovolak , Tenole Penfuenoreno novolak, Polymenole cuff. Tan, Polysanolide, 2, 4, 6 Tris (Dimethinole Minomechinole) Fenole, 2, 4, 6-Tris (dimethylaminomethyl) phenol-tri-2-ethylhexylate, Benzenoredimethylamine, 2- ( Dimethylaminomethinole) Phenol 2-Methylimidazole, 2-Ethyl-4-Methylimidazole 2-Undecylimidazole, 2-Heptadecylimidazole, 2-Phenilimidazole, 1 Monobenzyl 2-Methylimidazole, 1-Chianoethyl- 2 Methylimidazole, 2, 4 Diamino-6- (2 Methylimidazolyl (1)) -Ethyl S Triazine, BF Monoethylamine Complex, Noreise Acid Complex, Organic Acid Hydrazi , Diaminomaleonitrile, melamine derivative, imidazole derivative, polyamine salt, amine imide compound, aromatic diazonium salt, diarylodonium salt, triallylsulfonium salt, triarylselenium salt, ketimine compound Etc.

[0129] これらの硬化剤及び/又は硬化促進剤は、溶液の塗布性、基板やめつき膜との密 着性などの観点から、溶剤を除去した残りの不揮発成分の 0〜50質量％程度まで添 カロすること力 S好ましい。また、硬化剤及び/又は硬化促進剤は重合開始層に添加し てもよく、その場合は、重合開始層に添加した量とポリマー層中に添加した総和量で 上記範囲を満たすことが好ましレ、。  [0129] These curing agents and / or curing accelerators are used in an amount of about 0 to 50% by mass of the remaining non-volatile components from which the solvent has been removed from the viewpoints of solution applicability, adhesion to substrates and adhesive films, and the like. Ability to add S is preferable. Further, the curing agent and / or curing accelerator may be added to the polymerization initiation layer, and in that case, it is preferable that the above range is satisfied by the amount added to the polymerization initiation layer and the total amount added to the polymer layer. Les.

[0130] また、更に、ゴム成分（ί列えば、 carboxyl terminated butadiene acrylonitrile (CTBN ) )、難燃化剤 (例えば、りん系難燃化剤）、希釈剤やチキソトロピー化剤、顔料、消泡 剤、レべリング剤、カップリング剤などを添加してもよい。また、これらの添加剤は必要 に応じて重合開始層に添加してもよい。  [0130] Further, rubber components (for example, carboxyl terminated butadiene acrylonitrile (CTBN)), flame retardants (for example, phosphorus flame retardants), diluents, thixotropic agents, pigments, antifoaming agents A leveling agent, a coupling agent, or the like may be added. Further, these additives may be added to the polymerization initiation layer as necessary.

[0131] これらの重合性基及び相互作用性基を有する化合物と各種の添加剤とを適宜混 合した組成物を用いることで、形成されたポリマー層の物性、例えば、熱膨張係数、 ガラス転移温度、ヤング率、ポアソン比、破断応力、降伏応力、熱分解温度などを最 適に設定することができる。特に、破断応力、降伏応力、熱分解温度については、よ り高い方が好ましい。  [0131] By using a composition in which these compounds having a polymerizable group and an interactive group and various additives are appropriately mixed, the physical properties of the formed polymer layer, for example, thermal expansion coefficient, glass transition Temperature, Young's modulus, Poisson's ratio, breaking stress, yield stress, pyrolysis temperature, etc. can be set optimally. In particular, it is preferable that the breaking stress, yield stress, and thermal decomposition temperature are higher.

得られたポリマー層は、温度サイクル試験や熱経時試験、リフロー試験などで熱耐 久性を測定することができる。例えば、熱分解に関しては、 200°C環境に 1時間曝し た場合の質量減少が 20%以下であると、十分に熱耐久性を有していると評価できる  The obtained polymer layer can be measured for heat durability by a temperature cycle test, a thermal aging test, a reflow test, or the like. For example, with regard to thermal decomposition, if the mass loss when exposed to an environment of 200 ° C for 1 hour is 20% or less, it can be evaluated as having sufficient thermal durability.

[0132] 重合性基及び相互作用性基を有する化合物を含有する組成物を接触させる場合 には、その塗布量は、めっき触媒又はその前駆体との充分な相互作用形成性の観 点からは、固形分換算で、 0.；!〜 10g/m2が好ましぐ特に 0. 5〜5g/m2が好まし い。 [0132] When a composition containing a compound having a polymerizable group and an interactive group is brought into contact, the coating amount is from the viewpoint of sufficient interaction with the plating catalyst or its precursor. , in terms of solid content, 0;.! ~ 10g / m 2 is preferred tool especially 0. 5~5g / m 2 is not preferable.

なお、基板上に、重合性基及び相互作用性基を有する化合物を含有する組成物 を塗布し、乾燥させて、重合性基及び相互作用性基を有する化合物を含有する層を 形成する場合、塗布と乾燥との間に、 20〜40°Cで 0. 5〜2時間放置させて、残存す る溶剤を除去してもよい。 When a composition containing a compound having a polymerizable group and an interactive group is applied on a substrate and dried to form a layer containing a compound having a polymerizable group and an interactive group, Leave between 20 and 40 ° C for 0.5 to 2 hours between application and drying. The solvent may be removed.

[0133] エネルギーの付与 [0133] Giving energy

基板表面へのエネルギー付与方法としては、例えば、加熱や露光等の輻射線照射 を用いる方法が挙げられる。該方法の例としては、 UVランプ、可視光線などによる光 照射、ホットプレートなどを用いた加熱等が挙げられる。該方法に用いる光源としては 、例えば、水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、カーボンァ ーク灯、等が挙げられる。放射線の例としては、電子線、 X線、イオンビーム、遠赤外 線などが挙げられる。また、 g線、 i線、 Deep— UV光、高密度エネルギービーム（レ 一ザ一ビーム)も使用可能である。  Examples of a method for applying energy to the substrate surface include a method using radiation irradiation such as heating and exposure. Examples of the method include UV lamp, irradiation with visible light, etc., heating using a hot plate and the like. Examples of the light source used in the method include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far-infrared rays. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) can be used.

一般的に用いられる具体的な態様の例としては、熱記録ヘッド等による直接画像様 記録、赤外線レーザーによる走査露光、キセノン放電灯などの高照度フラッシュ露光 や赤外線ランプ露光などが好適に挙げられる。  Specific examples of specific modes that are generally used include direct image recording with a thermal recording head, scanning exposure with an infrared laser, high illumination flash exposure such as a xenon discharge lamp, and infrared lamp exposure.

エネルギー付与に要する時間は、 目的とするグラフトポリマーの生成量及び光源に より異なる力 通常、 10秒〜 5時間の間である。  The time required for energy application varies depending on the amount of the graft polymer produced and the light source, and is usually between 10 seconds and 5 hours.

[0134] なお、エネルギーの付与を露光にて行う場合、その露光パワーは、グラフト重合を 容易に進行させるため、また、生成されたグラフトポリマーの分解を抑制するため、 10 mj/ cm〜 5000mj/cmの範囲であることが好ましぐより好ましくは、 50mj/cm2 [0134] When energy is applied by exposure, the exposure power is 10 mj / cm to 5000 mj / in order to facilitate the progress of graft polymerization and to suppress the decomposition of the generated graft polymer. More preferably in the range of cm, 50 mj / cm 2

〜3000mj/cm2の範囲である。 It is in the range of ~3000mj / cm 2.

また、重合性基及び相互作用性基を有する化合物として、平均分子量 2万以上、 重合度 200量体以上のポリマーを使用すると、低エネルギーの露光でグラフト重合が 容易に進行するため、生成したグラフトポリマーの分解を更に抑制することができる。  In addition, when a polymer having an average molecular weight of 20,000 or more and a degree of polymerization of 200 or more is used as the compound having a polymerizable group and an interactive group, graft polymerization proceeds easily with low energy exposure. Degradation of the polymer can be further suppressed.

[0135] 以上説明した（al)工程により、基板上には、相互作用性基を有するグラフトポリマ 一からなるポリマー層（グラフトポリマー層）を形成すること力 Sできる。 [0135] By the step (al) described above, it is possible to form a polymer layer (graft polymer layer) made of a graft polymer having an interactive group on the substrate.

[0136] 得られたポリマー層力 例えば、 pH12のアルカリ性溶液に添加し、 1時間攪拌した ときの重合性基部位の分解が 50%以下である場合は、該ポリマー層に対して高アル カリ性溶液による洗浄を行うことができる。 [0136] The obtained polymer layer strength For example, when the decomposition of the polymerizable group portion is 50% or less when added to an alkaline solution at pH 12 and stirred for 1 hour, the polymer layer has high alkalinity. Cleaning with a solution can be performed.

[0137] (al ' )工程 [0137] (al ') process

本発明の第 2の表面金属膜材料の作製方法における（al， )工程では、基板上に、 シァノ基を有し、且つ、該基板と直接化学結合したポリマーからなるポリマー層を形 成する。 In the (al,) process in the second surface metal film material production method of the present invention, on the substrate, A polymer layer made of a polymer having a cyano group and directly chemically bonded to the substrate is formed.

本工程は、前述の（al)工程における重合性基及び相互作用性基を有する化合物 として、重合性基及びシァノ基を有する化合物を用いる以外は、（al)工程に記載の 方法と同様の方法が用いられ、また、好ましい態様も同様である。  This step is a method similar to the method described in step (al) except that a compound having a polymerizable group and a cyano group is used as the compound having a polymerizable group and an interactive group in step (al) described above. Are also used, and preferred embodiments are also the same.

この（al ' )工程により、基板上には、シァノ基を有するグラフトポリマーからなるポリ マー層（グラフトポリマー層）を形成すること力 Sできる。  By this (al ′) step, it is possible to form a polymer layer (graft polymer layer) made of a graft polymer having a cyano group on the substrate.

[0138] 本工程で得られたポリマー層を構成するポリマーは、めっき触媒又はその前駆体と 相互作用を形成する官能基としてシァノ基を有する。このシァノ基は、前述の通り、極 性が高ぐめっき触媒等への吸着能が高いが、解離性の極性基 (親水性基）のように 高い吸水性、親水性を有するものではないため、このシァノ基有するグラフトポリマー からなるポリマー層は、吸水性が低ぐ且つ、疎水性が高いものとなる。  [0138] The polymer constituting the polymer layer obtained in this step has a cyano group as a functional group that forms an interaction with the plating catalyst or its precursor. As described above, this cyano group has a high adsorption ability to a plating catalyst having a high polarity, but it does not have a high water absorption and hydrophilicity like a dissociative polar group (hydrophilic group). The polymer layer composed of the graft polymer having a cyano group has low water absorption and high hydrophobicity.

[0139] (a2)工程  [0139] (a2) Process

(a2)工程では、上記（al)又は（al ' )工程において形成されたポリマー層に、めつ き触媒又はその前駆体を付与する。本工程においては、ポリマー層を構成するダラ フトポリマーが有する相互作用性基 (シァノ基）が、その機能に応じて、付与されため つき触媒又はその前駆体を付着（吸着)する。  In the step (a2), a catalyst or a precursor thereof is added to the polymer layer formed in the step (al) or (al ′). In this step, an interactive group (cyan group) possessed by the draft polymer that constitutes the polymer layer is given according to its function, and attaches (adsorbs) the catalyst or precursor thereof.

ここで、めっき触媒又はその前駆体としては、後述する（a3)めっき工程における、 めっきの触媒や電極として機能するものが挙げられる。そのため、めっき触媒又はそ の前駆体は、 (a3)めっき工程におけるめっきの種類により決定される。  Here, examples of the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in the plating step (a3) described later. Therefore, the plating catalyst or its precursor is determined by (a3) the type of plating in the plating step.

なお、ここで、本工程において用いられるめっき触媒又はその前駆体は、無電解め つき触媒又はその前駆体であることが好ましい。  Here, the plating catalyst or its precursor used in this step is preferably an electroless plating catalyst or its precursor.

[0140] 無電解めつき触媒 [0140] Electroless catalyst

本発明にお!/、て用いられる無電解めつき触媒は、無電解めつき時の活性核となるも のであれば、如何なるものも用いること力 Sできる。その例としては、自己触媒還元反応 の触媒能を有する金属（Nはりイオン化傾向の低い無電解めつきできる金属として知 られるもの）などが挙げられる。具体例としては、 Pd、 Ag、 Cu、 Ni、 Al、 Fe、 Coなど 力 S挙げられる。中でも、多座配位可能なものが好ましい。特に、配位可能な官能基の 種類数、触媒能の高さから、 Pdが好ましい。 Any electroless catalyst used in the present invention can be used as long as it becomes an active nucleus during electroless plating. Examples thereof include metals having catalytic ability for autocatalytic reduction reactions (known as metals capable of electroless plating with a low N-beam ionization tendency). Specific examples include forces S such as Pd, Ag, Cu, Ni, Al, Fe, and Co. Among them, those capable of multidentate coordination are preferable. Especially for functional groups that can be coordinated Pd is preferred because of the number of types and high catalytic ability.

この無電解めつき触媒は、金属コロイドとして用いてもよい。一般に、金属コロイドは This electroless plating catalyst may be used as a metal colloid. In general, metal colloids

、荷電を持った界面活性剤又は荷電を持った保護剤が存在する溶液中にお!、て、 金属イオンを還元することにより作製することができる。金属コロイドの荷電は、ここで 使用される界面活性剤又は保護剤により調節することができる。 It can be prepared by reducing a metal ion in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be controlled by the surfactant or protective agent used here.

[0141] 無電解めつき触媒前駆体  [0141] Electroless plating catalyst precursor

本工程において用いられる無電解めつき触媒前駆体としては、化学反応により無電 解めつき触媒となりうるものであれば、特に制限なく使用することができる。主には、上 記無電解めつき触媒として挙げた金属の金属イオンが用いられる。無電解めつき触 媒前駆体である金属イオンは、還元反応により無電解めつき触媒である 0価金属にな る。無電解めつき触媒前駆体である金属イオンは、ポリマー層へ付与した後、無電解 めっき浴への浸漬前に、別途還元反応により 0価金属に変化させて無電解めつき触 媒としてもよいし、無電解めつき触媒前駆体のまま無電解めつき浴に浸漬し、無電解 めっき浴中の還元剤により金属（無電解めつき触媒）に変化させてもよい。  The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can be a nonelectrolytic plating catalyst by a chemical reaction. The metal ions of the metals mentioned above as the electroless plating catalyst are mainly used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion, which is an electroless plating catalyst precursor, may be applied to the polymer layer and then converted into a zero-valent metal by a reduction reaction before immersion in the electroless plating bath to form an electroless plating catalyst. Then, it may be immersed in an electroless plating bath as the electroless plating catalyst precursor, and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

[0142] 実際には、無電解めつき前駆体である金属イオンは、金属塩を用いてポリマー層上 に付与する。使用される金属塩には、適切な溶媒に溶解して金属イオンと塩基（陰ィ オン）とに解離されるものであれば特に制限はない。具体例としては、 M (NO ) 、 M  [0142] In practice, the metal ion, which is an electroless plating precursor, is applied onto the polymer layer using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in an appropriate solvent and can be dissociated into a metal ion and a base (anion). Specific examples include M (NO), M

3 n 3 n

Cln、 M (SO )、 M (PO ) (Mは、 n価の金属原子を表す）などが挙げられる。 Cln, M (SO), M (PO) (M represents an n-valent metal atom), and the like.

2/n 4 3/n 4  2 / n 4 3 / n 4

金属イオンとしては、上記の金属塩が解離したものを好適に用いることができる。具 体例としては、例えば、 Agイオン、 Cuイオン、 A1イオン、 Niイオン、 Coイオン、 Feィ オン、 Pdイオンが挙げられる。中でも、多座配位可能なものが好ましい。特に、配位 可能な官能基の種類数、及び触媒能の点で、 Pdイオンが好ましい。  As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include Ag ions, Cu ions, A1 ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable. In particular, Pd ions are preferred in terms of the number of types of functional groups capable of coordination and the catalytic ability.

[0143] 無電解めつき触媒である金属、或いは、無電解めつき前駆体である金属塩をポリマ 一層に付与する方法としては、金属を適当な分散媒に分散した分散液、或いは、金 属塩を適切な溶媒で溶解し、解離した金属イオンを含む溶液を調製し、その分散液 又は溶液をポリマー層上に塗布する力、、或いは、その分散液又は溶液中にポリマー 層が形成された基板を浸漬すればょレ、。 [0143] As a method for applying a metal that is an electroless plating catalyst or a metal salt that is an electroless plating precursor to a polymer layer, a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a metal is used. The salt was dissolved in an appropriate solvent to prepare a solution containing dissociated metal ions, and the dispersion or solution was applied onto the polymer layer, or the polymer layer was formed in the dispersion or solution. Soak the substrate.

また、（al)又は（al ' )工程において、表面グラフト重合法を用いる場合、基板上に 、重合性基及び相互作用性基 (シァノ基)を有する化合物を含有する組成物を接触 させるが、この組成物中に、無電解めつき触媒又はその前駆体を添加する方法を用 いてもよい。重合性基及び相互作用性基 (シァノ基）を有する化合物と、無電解めつ き触媒又はその前駆体と、を含有する組成物を、基板上に接触させて、表面グラフト 重合法を適用することにより、相互作用性基 (シァノ基)を有し、且つ、基板と直接化 学結合したポリマーと、めっき触媒又はその前駆体と、を含有するポリマー層を形成 すること力 Sできる。なお、この方法を用いれば、本発明における（al)又は（al ' )工程 と（a2)工程とが 1工程で行えることになる。 In the (al) or (al ') process, when surface graft polymerization is used, , A composition containing a compound having a polymerizable group and an interactive group (cyan group) is brought into contact, and a method of adding an electroless plating catalyst or a precursor thereof to the composition may be used. . A surface graft polymerization method is applied by contacting a composition containing a compound having a polymerizable group and an interactive group (cyan group) with an electroless plating catalyst or a precursor thereof on a substrate. Thus, it is possible to form a polymer layer containing a polymer having an interactive group (cyan group) and directly chemically bonded to the substrate, and a plating catalyst or a precursor thereof. If this method is used, the (al) or (al ′) step and the (a2) step in the present invention can be performed in one step.

[0144] なお、本発明の第 3の表面金属膜材料の作製方法における（al")工程を経ること で、樹脂フィルムの両面に対してポリマー層が形成されている場合には、その両面の ポリマー層に対して同時に無電解めつき触媒又はその前駆体を接触させるために、 上記の浸漬法を用いることが好ましレ、。  [0144] In the case where the polymer layer is formed on both surfaces of the resin film through the (al ") step in the third method for producing a metal film material of the present invention, In order to simultaneously contact the electroless catalyst or precursor thereof with the polymer layer, it is preferable to use the above immersion method.

[0145] 上記のように無電解めつき触媒又はその前駆体を接触させることで、ポリマー層中 の相互作用性基 (シァノ基）に、ファンデルワールス力のような分子間力による相互作 用、又は、孤立電子対による配位結合による相互作用を利用して、無電解めつき触 媒又はその前駆体を吸着させることができる。  [0145] By contacting the electroless plating catalyst or its precursor as described above, the interaction group (Cyan group) in the polymer layer interacts with an intermolecular force such as van der Waals force. Alternatively, the electroless plating catalyst or its precursor can be adsorbed by utilizing the interaction due to the coordinate bond by the lone pair of electrons.

このような吸着を充分に行なわせるという観点からは、分散液、溶液、組成物中の 金属濃度、又は溶液中の金属イオン濃度は、 0. 00；!〜 50質量％の範囲であること が好ましぐ 0. 005〜30質量％の範囲であることが更に好ましい。また、接触時間と しては、 30秒〜 24時間程度であることが好ましぐ 1分〜 1時間程度であることがより 好ましい。  From the viewpoint of sufficiently carrying out such adsorption, the metal concentration in the dispersion, solution, or composition, or the metal ion concentration in the solution may be in the range of 0.00; The range of 0.005 to 30% by mass is more preferable. Further, the contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.

[0146] その他の触媒  [0146] Other catalysts

本発明において、後述の（a3)工程において、ポリマー層に対して、無電解めつきを 行わず直接電気めつきを行うために用いられる触媒としては、 0価金属を使用するこ とができる。この 0価金属の例としては、 Pd、 Ag、 Cu、 Ni、 Al、 Fe、 Coなどが挙げら れる。中でも、多座配位可能なものが好ましい。特に、相互作用性基 (シァノ基）に対 する吸着（付着)性、触媒能の高さから、 Pd、 Ag、 Cuが好ましい。  In the present invention, a zero-valent metal can be used as a catalyst used for direct electroplating without performing electroless plating on the polymer layer in the step (a3) described later. Examples of the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among them, those capable of multidentate coordination are preferable. In particular, Pd, Ag, and Cu are preferred because of their high adsorptive (adhesive) property to interactive groups (cyan groups) and high catalytic ability.

[0147] 以上説明した（a2)工程を経ることで、ポリマー層中の相互作用性基 (シァノ基）とめ つき触媒又はその前駆体との間に相互作用を形成することができる。 [0147] Through the step (a2) described above, the interaction group (cyan group) in the polymer layer is identified. An interaction can be formed between the catalyst and its precursor.

[0148] (a3)工程 [0148] (a3) Process

(a3)工程では、無電解めつき触媒又はその前駆体が付与されたポリマー層に対し 、めっきを行うことで、めっき膜が形成される。形成されためつき膜は、優れた導電性 、密着性を有する。  In the step (a3), a plating film is formed by plating the polymer layer to which the electroless plating catalyst or its precursor is applied. The formed adhesive film has excellent conductivity and adhesion.

本工程において行われるめっきの種類は、無電解めつき、電気めつき等が挙げられ 、前記（a2)工程において、ポリマー層との間に相互作用を形成しためっき触媒又は その前駆体の機能によって、選択することができる。  Examples of the type of plating performed in this step include electroless plating, electric plating, etc. In the step (a2), depending on the function of the plating catalyst or its precursor that has formed an interaction with the polymer layer. Can be selected.

つまり、本工程では、めっき触媒又はその前駆体が付与されたポリマー層に対し、 電気めつきを行ってもょレ、し、無電解めつきを行ってもょレ、。  In other words, in this process, electroplating or electroless plating can be applied to the polymer layer to which the plating catalyst or its precursor has been applied.

中でも、本発明においては、ポリマー層中に発現するハイブリッド構造の形成性及 び密着性向上の点から、無電解めつきを行うことが好ましい。また、所望の膜厚のめ つき層を得るために、無電解めつきの後に、更に電気めつきを行うことがより好ましい 態様である。  Among them, in the present invention, electroless plating is preferably performed from the viewpoint of the formation of a hybrid structure expressed in the polymer layer and the improvement of adhesion. In addition, in order to obtain a plating layer having a desired film thickness, it is a more preferable embodiment that electrical plating is further performed after electroless plating.

以下、本工程にぉレ、て好適に行われるめっきにつ!/、て説明する。  Hereinafter, plating that is suitably performed in this process will be described.

[0149] 無電解めつき [0149] Electroless plating

無電解めつきとは、めっきとして析出させたい金属イオンを溶力、した溶液を用いて、 化学反応によって金属を析出させる操作のことをレ、う。  Electroless plating refers to the operation of depositing metal by chemical reaction using a solution in which the metal ions to be deposited as a plating solution are dissolved.

本工程における無電解めつきは、例えば、無電解めつき触媒が付与された基板を、 水洗して余分な無電解めつき触媒 (金属）を除去した後、無電解めつき浴に浸漬して 行なう。使用される無電解めつき浴としては一般的に知られている無電解めつき浴を 使用すること力でさる。  The electroless plating in this process is performed, for example, by rinsing a substrate to which an electroless plating catalyst has been added to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. Do. The electroless bath used is the power of using a generally known electroless bath.

また、無電解めつき触媒前駆体が付与された基板を、無電解めつき触媒前駆体が ポリマー層に吸着又は含浸した状態で無電解めつき浴に浸漬する場合には、基板を 水洗して余分な前駆体 (金属塩など）を除去した後、無電解めつき浴中へ浸漬される 。この場合には、無電解めつき浴中において、めっき触媒前駆体の還元とこれに引き 続き無電解めつきが行われる。ここで使用される無電解めつき浴としても、上記同様、 一般的に知られている無電解めつき浴を使用することができる。 なお、無電解めつき触媒前駆体の還元は、上記のような無電解めつき液を用いる態 様とは別に、触媒活性化液 (還元液）を準備し、無電解めつき前の別工程として行うこ とも可能である。触媒活性化液は、無電解めつき触媒前駆体（主に金属イオン)を 0 価金属に還元できる還元剤を溶解した液であり、液全体に対する該前駆体の濃度がIn addition, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath with the electroless plating catalyst precursor adsorbed or impregnated in the polymer layer, the substrate is washed with water. After removing the excess precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless bath used here, a generally known electroless bath may be used as described above. In addition to reducing the electroless plating catalyst precursor, a catalyst activation solution (reducing solution) is prepared separately from the above-described method using the electroless plating solution. It is also possible to do as The catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to a zerovalent metal is dissolved, and the concentration of the precursor with respect to the entire liquid is

0. 1質量％〜50質量％の範囲にあることが一般的であり、 1 %〜30%の範囲にある ことが好ましい。使用可能な還元剤の例としては、水素化ホウ素ナトリウム、ヂメチノレ ァミンボランのようなホウ素系還元剤、ホルムアルデヒド、次亜リン酸などの還元剤が 挙げられる。 It is generally in the range of 1% to 50% by weight, preferably in the range of 1% to 30%. Examples of usable reducing agents include boron reducing agents such as sodium borohydride and dimethylolamine borane, and reducing agents such as formaldehyde and hypophosphorous acid.

[0150] 一般的な無電解めつき浴の組成としては、溶剤の他に、 1.めっき用の金属イオン、 2.還元剤、 3.金属イオンの安定性を向上させる添加剤（安定剤）が主に含まれてい る。このめつき浴には、これらに加えて、めっき浴の安定剤など公知の添加物が含ま れていてもよい。  [0150] The composition of a general electroless plating bath includes, in addition to the solvent, 1. metal ions for plating, 2. reducing agents, 3. additives that improve the stability of metal ions (stabilizers) Is mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.

[0151] このめつき浴に用いられる溶剤には、吸水性が低ぐ疎水性の高いポリマー層（前 記 1〜4の条件を全て満たすポリマー層）に対して、親和性の高い有機溶剤を含有さ せること力 S好ましい。有機溶剤の種類の選択や、含有量は、ポリマー層の物性に応じ て調製すればよい。特に、ポリマー層の条件 1における飽和吸水率が大きければ大 きいほど、有機溶剤の含有率を小さくすることが好ましい。具体的には、以下の通りで ある。  [0151] For the solvent used in this bath, an organic solvent having a high affinity for a highly hydrophobic polymer layer with low water absorption (a polymer layer that satisfies all of the above conditions 1 to 4) is used. Power of inclusion S is preferable. The selection and content of the organic solvent may be adjusted according to the physical properties of the polymer layer. In particular, the larger the saturated water absorption in the condition 1 of the polymer layer, the smaller the organic solvent content is preferred. Specifically, it is as follows.

即ち、条件 1における飽和吸水率が 0. 01 -0. 5質量％の場合、めっき浴の全溶 剤中の有機溶剤の含有量は 20〜80質量％であることが好ましぐ同飽和吸水率が 0 . 5〜5質量％の場合、めっき浴の全溶剤中の有機溶剤の含有量は 10〜80質量％ であること力 S好ましく、同飽和吸水率が 5〜； 10質量％の場合、めっき浴の全溶剤中の 有機溶剤の含有量は 0〜60質量％であることが好ましぐ同飽和吸水率が 10〜20 質量％の場合、めっき浴の全溶剤中の有機溶剤の含有量は 0〜45質量％であるこ とが好ましい。  That is, when the saturated water absorption rate in Condition 1 is 0.01 to 0.5% by mass, it is preferable that the content of the organic solvent in the total solution of the plating bath is 20 to 80% by mass. When the rate is 0.5 to 5% by mass, the content of the organic solvent in the total solvent of the plating bath is 10 to 80% by mass. S is preferable. When the saturated water absorption is 5 to 10% by mass. When the saturated water absorption is 10 to 20% by mass, it is preferable that the content of the organic solvent in the total solvent of the plating bath is 0 to 60% by mass. The amount is preferably 0 to 45% by mass.

めっき浴に用いられる有機溶剤としては、水に可能な溶媒である必要があり、その 点から、アセトンなどのケトン類、メタノール、エタノール、イソプロパノールなどのアル コール類が好ましく用いられる。 [0152] 無電解めつき浴に用いられる金属の種類としては、銅、すず、鉛、ニッケル、金、パ ラジウム、ロジウムが知られており、中でも、導電性の観点からは、銅、金が特に好ま しい。 The organic solvent used in the plating bath needs to be a solvent that can be used in water. From this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used. [0152] Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath. Of these, from the viewpoint of conductivity, copper and gold are used. Especially preferred.

また、上記金属に合わせて最適な還元剤、添加物がある。例えば、銅の無電解め つきの浴には、銅塩として CuSO、還元剤として HCOH、添加剤として銅イオンの安  In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless bath may contain CuSO as the copper salt, HCOH as the reducing agent, and copper ion as the additive.

4  Four

定剤である EDTAやロッシエル塩などのキレート剤、トリアルカノールァミンなどが含 まれている。また、 CoNiPの無電解めつきに使用されるめつき浴には、その金属塩と して硫酸コバルト、硫酸ニッケル、還元剤として次亜リン酸ナトリウム、錯化剤としてマ ロン酸ナトリウム、りんご酸ナトリウム、こはく酸ナトリウムが含まれている。また、パラジ ゥムの無電解めつき浴には、金属イオンとして（Pd (NH ) ) C1、還元剤として NH、  It contains chelating agents such as EDTA and Rossiel salt, trialkanolamine, which are regular agents. In addition, the metal bath used for electroless plating of CoNiP includes cobalt sulfate, nickel sulfate as a metal salt, sodium hypophosphite as a reducing agent, sodium malonate, malic acid as a complexing agent. Contains sodium and sodium succinate. In addition, palladium electroless baths include (Pd (NH)) C1 as metal ions, NH as a reducing agent,

3 4 2 3 3 4 2 3

H NNH、安定化剤として EDTAが含まれている。これらのめっき浴には、上記成分H NNH and EDTA as stabilizer. These plating baths contain the above ingredients

2 2 twenty two

以外の成分が入ってレ、てもよレ、。  Ingredients other than N

[0153] このようにして形成される無電解めつきによるめつき膜の膜厚は、めっき浴の金属ィ オン濃度、めっき浴への浸漬時間、或いは、めっき浴の温度などにより制御すること 力できる。導電性の観点からは、該膜厚は 0. 5 m以上であることが好ましぐ 3 ^ 111 以上であることがより好ましレ、。  [0153] The film thickness of the electroless plating formed in this way can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. it can. From the viewpoint of conductivity, the film thickness is preferably 0.5 m or more, more preferably 3 ^ 111 or more.

また、めっき浴への浸漬時間は、 1分〜 6時間程度であることが好ましぐ 1分〜 3時 間程度であることがより好ましレ、。  Also, the immersion time in the plating bath is preferably about 1 minute to 6 hours, more preferably about 1 minute to 3 hours.

[0154] 以上のようにして得られた無電解めつきによるめつき膜は、走査型電子顕微鏡（sea nning electron microscope： SEM)による断面観察により、ポリマー層中に無電解め つき触媒やめつき金属からなる微粒子が高密度で分散していること、また更にポリマ 一層上にめっき金属が析出していることが確認された。基板とめっき膜との界面は、 ポリマーと微粒子とのハイブリッド状態であるため、基板（有機成分）と無機物（触媒金 属又はめつき金属）との界面が平滑（例えば、凹凸差が 500nm以下）であっても、密 着性が良好となる。  [0154] The electroless plating film obtained as described above is obtained by cross-sectional observation with a scanning electron microscope (SEM) in the polymer layer. It was confirmed that the fine particles made of the above were dispersed at a high density, and that the plated metal was further deposited on the polymer layer. Since the interface between the substrate and the plating film is a hybrid state of polymer and fine particles, the interface between the substrate (organic component) and the inorganic material (catalyst metal or metal) is smooth (for example, the unevenness difference is 500 nm or less) Even so, the adhesion is good.

[0155] 電気めつき  [0155] Electric plating

本工程におレ、ては、（a2)工程にお!/、て付与されためつき触媒又はその前駆体が 電極としての機能を有する場合、その触媒又はその前駆体が付与されたポリマー層 に対して、電気めつきを行うことができる。 In this step, if the catalyst or its precursor applied in step (a2) has a function as an electrode, the polymer layer to which the catalyst or its precursor is applied On the other hand, it is possible to carry out electrical plating.

また、前述の無電解めつきの後、形成されためつき膜を電極とし、更に、電気めつき を行ってもよ!/、。これにより基板との密着性に優れた無電解めつき膜をベースとして、 そこに新たに任意の厚みをもつ金属膜を容易に形成することができる。このように、無 電解めつきの後に、電気めつきを行うことで、金属膜を目的に応じた厚みに形成しうる ため、本発明の金属膜を種々の応用に適用するのに好適である。  In addition, after the electroless plating described above, it is also possible to use a film formed as an electrode and then perform electroplating! /. As a result, it is possible to easily form a new metal film having an arbitrary thickness on the basis of the electroless plating film having excellent adhesion to the substrate. As described above, by performing electro-plating after electroless plating, the metal film can be formed with a thickness according to the purpose, and therefore, the metal film of the present invention is suitable for various applications.

[0156] 本発明における電気めつきの方法としては、従来公知の方法を用いることができる 。なお、本工程の電気めつきに用いられる金属の例としては、銅、クロム、鉛、ニッケ ノレ、金、銀、すず、亜鉛などが挙げられる。導電性の観点から、銅、金、銀が好ましく 、銅がより好ましい。 [0156] As a method of electroplating in the present invention, a conventionally known method can be used. Examples of metals used for electroplating in this step include copper, chromium, lead, nickel gnole, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is more preferable.

[0157] 電気めつきにより得られる金属膜の膜厚は、用途に応じて異なるものであり、めっき 浴中に含まれる金属濃度、或いは、電流密度などを調整することでコントロールする ことができる。なお、一般的な電気配線などに用いる場合の膜厚は、導電性の観点 から、 0. 5 m以上であることが好ましぐ 3 m以上であることがより好ましい。  [0157] The thickness of the metal film obtained by electroplating varies depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath or the current density. The film thickness when used for general electric wiring is preferably 0.5 m or more, more preferably 3 m or more from the viewpoint of conductivity.

[0158] 本発明において、前述のめっき触媒、めっき触媒前駆体に由来する金属や金属塩 、及び/又は、無電解めつきにより、ポリマー層中に析出した金属が、該層中でフラク タル状の微細構造体として形成されていることによって、金属膜とポリマー層との密着 性を更に向上させることができる。  [0158] In the present invention, the metal or metal salt derived from the above-described plating catalyst, plating catalyst precursor, and / or metal deposited in the polymer layer by electroless plating is fractal in the layer. By being formed as a fine structure, the adhesion between the metal film and the polymer layer can be further improved.

ポリマー層中に存在する金属量は、基板断面を金属顕微鏡にて写真撮影したとき 、ポリマー層の最表面から深さ 0. 5〃mまでの領域に占める金属の割合が 5〜50面 積％であり、ポリマー層と金属界面の算術平均粗さ Ra (ISO 4288 ( 1996) )が 0. 05 μ m〜0. 5 mである場合に、更に強い密着力が発現される。  The amount of metal present in the polymer layer is 5 to 50% by area when the cross section of the substrate is photographed with a metal microscope, and the proportion of the metal in the region from the outermost surface of the polymer layer to a depth of 0.5 mm is Further, when the arithmetic average roughness Ra (ISO 4288 (1996)) between the polymer layer and the metal interface is 0.05 μm to 0.5 m, a stronger adhesion force is expressed.

[0159] 表面金属膜材料  [0159] Surface metal film material

本発明の表面金属膜材料の作製方法の各工程を経ることで、本発明の表面金属 膜材料を得ること力できる。なお、本発明の第 3の表面金属膜材料の作製方法を適 用すれば、両面に金属膜が形成された表面金属膜材料を得ることができる。  Through the steps of the method for producing the surface metal film material of the present invention, the surface metal film material of the present invention can be obtained. If the third method for producing a surface metal film material of the present invention is applied, a surface metal film material having a metal film formed on both surfaces can be obtained.

本発明の表面金属膜材料の作製方法により得られた表面金属膜材料は、高温高 湿下であっても、金属膜の密着力の変動が少ないといった効果を有する。この表面 金属膜材料は、例えば、電磁波防止膜、コーティング膜、 2層 CCL (Copper Clad La minate)材料、電気配線用材料等の種々の用途に適用することができる。 The surface metal film material obtained by the method for producing a surface metal film material of the present invention has an effect that there is little fluctuation in the adhesion of the metal film even under high temperature and high humidity. This surface The metal film material can be applied to various uses such as an electromagnetic wave prevention film, a coating film, a two-layer CCL (Copper Clad Laminate) material, and an electric wiring material.

[0160] 本発明の金属パターン材料の作製方法は、（al)〜（a3)の工程を経て得られた本 発明の表面金属膜材料のめっき膜をパターン状にエッチングする工程を有する。 この（a4)エッチング工程につ!/、て以下に説明する。 [0160] The method for producing the metal pattern material of the present invention includes a step of etching the plating film of the surface metal film material of the present invention obtained through the steps (al) to (a3) into a pattern. The (a 4) an etching step Nitsu! /, Te is described below.

[0161] (a4)工程  [0161] (a4) Process

(a4)工程では、上記 (a3)工程で形成されためつき膜 (金属膜)をパターン状にエツ チングする。即ち、本工程では、基板表面全体に形成されためつき膜の不要部分を エッチングで取り除くことで、所望の金属パターンを形成することができる。  In the step (a4), the padding film (metal film) formed in the step (a3) is etched into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the cover film formed on the entire substrate surface by etching.

この金属パターンの形成には、如何なる手法も使用することができ、具体的には一 般的に知られているサブトラクティブ法、セミアディティブ法が用いられる。  Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.

[0162] サブトラクティブ法とは、形成されためつき膜上にドライフィルムレジスト層を設けパ ターン露光、現像により金属パターン部と同じパターンを形成し、ドライフィルムレジス トパターンをマスクとしてエッチング液でめっき膜を除去し、金属パターンを形成する 方法である。ドライフィルムレジストとしては如何なる材料も使用でき、ネガ型、ポジ型 、液状、フィルム状のものが使用できる。また、エッチング方法としては、プリント配線 基板の製造時に使用されている方法が何れも使用可能であり、湿式エッチング、ドラ ィエッチング等が使用可能であり、任意に選択すればよい。作業の操作上、装置など が簡便であることから、湿式エッチングが好ましい。使用可能なエッチング液の例とし ては、塩化第二銅、塩化第二鉄等の水溶液が挙げられる。 [0162] In the subtractive method, a dry film resist layer is provided on the deposited film, the same pattern as the metal pattern is formed by pattern exposure and development, and plating is performed with an etching solution using the dry film resist pattern as a mask. This is a method of removing a film and forming a metal pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like materials can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In view of the operation, wet etching is preferable because the apparatus is simple. Examples of usable etching solutions include aqueous solutions of cupric chloride and ferric chloride.

[0163] また、セミアディティブ法とは、形成されためつき膜上にドライフィルムレジスト層を設 け、パターン露光、現像により非金属パターン部と同じパターンを形成し、ドライフィ ルムレジソトパターンをマスクとして電気めつきを行い、ドライフィルムレジソトパターン を除去した後にクイックエッチングを実施し、めっき膜をパターン状に除去することに より、金属パターンを形成する方法である。ドライフィルムレジソト、エッチング液等の 材料としては、サブトラクティブ法におけると同様の材料が使用できる。また、電気め つき手法としては前記記載の手法が使用できる。  [0163] In addition, the semi-additive method is a method in which a dry film resist layer is provided on a coating film to be formed, and the same pattern as a non-metallic pattern portion is formed by pattern exposure and development, and the dry film resist pattern is used as a mask. This is a method of forming a metal pattern by performing electrical etching, removing the dry film resist pattern, performing quick etching, and removing the plating film in a pattern. As materials such as dry film resist and etching solution, the same materials as in the subtractive method can be used. Moreover, the method described above can be used as the electroplating method.

[0164] 以上の（al)〜（a4)工程を経ることにより、所望の金属パターンを有する金属パタ ーン材料が作製される。 [0164] A metal pattern having a desired metal pattern is obtained through the above steps (al) to (a4). The material is made.

一方、（al)又は（al， )の工程で得られるポリマー層をパターン状に形成し、パター ン状のポリマー層に対し（a2)、及び（a3)工程を行うことで、金属パターン材料を作

Figure imgf000053_0001
On the other hand, by forming the polymer layer obtained in the step (al) or (al,) in a pattern and performing the steps (a2) and (a3) on the pattern polymer layer, the metal pattern material is obtained. Product
Figure imgf000053_0001

(al)又は（al ' )の工程で得られるポリマー層をパターン状に形成する方法としては 、具体的には、ポリマー層を形成する際に付与されるエネルギーをパターン状とすれ ばよく、また、エネルギーを付与しない部分を現像で除去することでパターン状のポリ マー層を形成することができる。  As a method for forming the polymer layer obtained in the step (al) or (al ′) into a pattern, specifically, the energy applied when forming the polymer layer may be changed into a pattern. Then, a pattern-like polymer layer can be formed by removing a portion to which energy is not applied by development.

なお、現像方法としては、重合性基及び相互作用性基 (シァノ基)を有する化合物 などのポリマー層を形成するために用いられる材料を溶解しうる溶剤に浸漬すること で行われる。浸漬する時間は 1分〜 30分の範囲にあることが好ましい。  The developing method is carried out by immersing a material used for forming a polymer layer such as a compound having a polymerizable group and an interactive group (cyan group) in a solvent capable of dissolving. The immersion time is preferably in the range of 1 minute to 30 minutes.

また、（al)又は（al ' )のポリマー層は、グラビア印刷法、インクジェット法、マスクを 用いたスプレーコート法など公知の塗布方法で直接パターユングした後、エネルギ 一付与し、その後、現像することで形成してもよい。  In addition, the polymer layer (al) or (al ′) is directly patterned by a known coating method such as gravure printing, ink jet method, spray coating method using a mask, and then given energy, and then developed. You may form by.

ノ ターン形成したポリマー層上にめっき膜を形成するための（a2)、及び (a3)工程 は、前述の方法と同じである。  Steps (a2) and (a3) for forming a plating film on the polymer layer formed with the pattern are the same as those described above.

[0166] 金属パターン材料 [0166] Metal pattern material

本発明の金属パターン材料は、前述の本発明の金属パターン材料の作製方法に より得られたものである。  The metal pattern material of the present invention is obtained by the above-described method for producing a metal pattern material of the present invention.

得られた金属パターン材料を構成するポリマー層は、前述のように、吸水性が低ぐ 疎水性が高いため、このポリマー層の露出部（金属パターンの非形成領域）は、絶縁 信頼性に優れる。  As described above, since the polymer layer constituting the obtained metal pattern material has low water absorption and high hydrophobicity, the exposed portion of the polymer layer (the metal pattern non-formation region) is excellent in insulation reliability. .

[0167] 本発明の金属パターン材料は、表面の凹凸差が 500nm以下はり好ましくは 100η m以下）の基板上の全面又は局所的に、金属膜（めっき膜)を設けたものであることが 好ましい。また、基板と金属パターンとの密着性が 0. 2kN/m以上であることが好ま しい。即ち、基板表面が平滑でありながら、基板と金属パターンとの密着性に優れる ことを特徴とする。  [0167] The metal pattern material of the present invention preferably has a metal film (plating film) provided on the entire surface or locally on the substrate having a surface unevenness difference of 500 nm or less (preferably 100 ηm or less). . In addition, the adhesion between the substrate and the metal pattern is preferably 0.2 kN / m or more. That is, the substrate surface is smooth, but the adhesion between the substrate and the metal pattern is excellent.

[0168] なお、基板表面の凹凸差は、基板を基板表面に対して垂直に切断し、その断面を SEMにより観察することにより測定した値である。 [0168] Note that the unevenness difference on the substrate surface is obtained by cutting the substrate perpendicularly to the substrate surface and It is the value measured by observing with SEM.

より詳細には、 ISO 4287 (1997)に準じて測定した基板表面の Rz、即ち、「指定面に おける、最大から 5番目までの山頂の Zデータの平均値と、最小から 5番目までの谷 底の平均値との差」が、 500nm以下であることが好ましい。  More specifically, Rz of the substrate surface measured according to ISO 4287 (1997), that is, “the average value of the Z data of the highest to fifth peaks and the lowest to fifth valleys on the specified surface. The “difference from the average value of the bottom” is preferably 500 nm or less.

また、基板と金属膜との密着性の値は、金属膜 (金属パターン)の表面に、銅板 (厚 さ： 0. lmm)をエポキシ系接着剤（商品名：ァラルダイト、チバガイギー製）で接着し、 140°Cで 4時間乾燥した後、 JIS C 6481 (IEC 60249-1 (1982)に準拠する公知のプ リント配線板用銅張積層板試験方法）に基づき 90度剥離実験を行うか、又は、金属 膜自体の端部を直接剥ぎ取り、 JIS C 6481に基づき 90度剥離実験を行って得られ たィ直である。  The adhesion value between the substrate and the metal film is determined by bonding a copper plate (thickness: 0.1 mm) to the surface of the metal film (metal pattern) with an epoxy adhesive (trade name: Araldite, manufactured by Ciba Geigy). After drying at 140 ° C for 4 hours, perform a 90-degree peeling experiment based on JIS C 6481 (a known test method for copper-clad laminates for printed wiring boards in accordance with IEC 60249-1 (1982)), or This is a straight line obtained by directly peeling off the end of the metal film itself and conducting a 90-degree peeling test based on JIS C 6481.

[0169] 本発明の金属パターン材料の作製方法により得られた金属パターン材料は、例え ば、半導体チップ、各種電気配線板、 FPC (Flexible Print Circuit)、 COF (Chip On Film)、 TAB (Tape Automated Bonding)、アンテナ、多層配泉基板、マザ一ボード、 等の種々の用途に適用することができる。  [0169] The metal pattern material obtained by the method for producing a metal pattern material of the present invention includes, for example, a semiconductor chip, various electric wiring boards, FPC (Flexible Print Circuit), COF (Chip On Film), TAB (Tape Automated). Bonding), antenna, multilayer spring board, mother board, etc.

[0170] 新規ポリマー  [0170] New polymer

本発明の一態様として提供される新規ポリマーは、下記式（1)で表されるユニット、 及び、下記式（2)で表されるユニットを含む共重合体である。該新規ポリマーは、本 発明の一態様である表面金属膜材料の作製方法において用いられる前記のシァノ 基含有重合性ポリマーの好適な例の一つである。以下、該新規ポリマーを、適宜、「 二トリル基含有重合性ポリマー」と称して、詳細に説明する。  The novel polymer provided as one embodiment of the present invention is a copolymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2). The novel polymer is one of the preferred examples of the above-mentioned cyano group-containing polymerizable polymer used in the method for producing a surface metal film material which is one embodiment of the present invention. Hereinafter, the novel polymer will be described in detail by appropriately referring to a “nitrile group-containing polymerizable polymer”.

[0171] [化 16] [0171] [Chemical 16]

Figure imgf000055_0001
式 （ 1 ) 式 ( X cL1—2 )
Figure imgf000055_0001
Formula (1) Formula (XcL1-2)

2卜  2 卜

[0172] 上記式（1)及び式（2)中、！^〜 は、各々独立に、水素原子、又は置換もしくは無 置換のアルキル基を表し、 X、 Y及び Zは、各々独立に、単結合、置換もしくは無置換 の二価の有機基、エステル基、アミド基、又はエーテル基を表し、 L1及び L2は、各々 独立に、置換もしくは無置換の二価の有機基を表す。 [0172] In the above formula (1) and formula (2),! ^ ~ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y and Z each independently represent a single bond, a substituted or unsubstituted divalent organic group, an ester group, It represents an amide group or an ether group, and L 1 and L 2 each independently represent a substituted or unsubstituted divalent organic group.

[0173] 1〜!^が、置換もしくは無置換のアルキル基である場合、無置換のアルキル基とし ては、メチル基、ェチル基、プロピル基、ブチル基が挙げられ、また、置換アルキル基 としては、メトキシ基、ヒドロキシ基、塩素原子、臭素原子、フッ素原子等で置換された 、メチル基、ェチル基、プロピル基、ブチル基が挙げられる。 [0173] When 1 to! ^ Is a substituted or unsubstituted alkyl group, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Includes a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.

なお、 R1としては、水素原子、メチル基、或いは、ヒドロキシ基又は臭素原子で置換 されたメチル基が好ましい。 R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

R2としては、水素原子、メチル基、或いは、ヒドロキシ基又は臭素原子で置換された メチル基が好ましい。 R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

R3としては、水素原子が好ましい。 R 3 is preferably a hydrogen atom.

R4としては、水素原子が好ましい。 R 4 is preferably a hydrogen atom.

R5としては、水素原子、メチル基、或いは、ヒドロキシ基又は臭素原子で置換された メチル基が好ましい。 R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

[0174] X、 Y及び Zが、置換もしくは無置換の二価の有機基の場合、該二価の有機基とし ては、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換の芳香族炭化 水素基が挙げられる。 [0174] When X, Y and Z are a substituted or unsubstituted divalent organic group, the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic group. Family carbonization A hydrogen group is mentioned.

置換もしくは無置換の脂肪族炭化水素基としては、メチレン基、エチレン基、プロピ レン基、ブチレン基、又はこれらの基が、メトキシ基、ヒドロキシ基、塩素原子、臭素原 子、フッ素原子等で置換されたものが好ましい。  As a substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or these groups are substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like. The ones made are preferred.

置換もしくは無置換の芳香族炭化水素基としては、無置換のフエニル基、若しくは 、メトキシ基、ヒドロキシ基、塩素原子、臭素原子、フッ素原子等で置換されたフエ二 ル基が好ましい。  The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.

中でも、一（CH ) — (nは 1〜3の整数）が好ましぐ更に好ましくは一 CH—である  Among them, one (CH 3) — (n is an integer of 1 to 3) is preferable, and one CH— is more preferable.

2 n 2 2 n 2

〇 Yes

[0175] L1は、ウレタン結合又はウレァ結合を有する二価の有機基であることが好ましぐゥ レタン結合を有する二価の有機基であることがより好ましぐ中でも、総炭素数;!〜 9 であるものが好ましい。なお、ここで、 L1の総炭素数とは、 L1で表される置換もしくは 無置換の二価の有機基に含まれる総炭素原子数を意味する。 [0175] L 1 is preferably a divalent organic group having a urethane bond or a urea bond, and even more preferably a divalent organic group having a urethane bond. ! ~ 9 are preferred. Incidentally, the total number of carbon atoms of L 1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 1.

より具体的には、 L1の構造は、下記式（1 1)、又は、式（1 2)で表される構造で あることが好ましい。 More specifically, the structure of L 1 is preferably a structure represented by the following formula (11) or formula (12).

[0176] [化 17]

Figure imgf000056_0001
[0176] [Chemical 17]
Figure imgf000056_0001

式 ( 1 1 ) 式 （ 1— 2 )  Formula (1 1) Formula (1− 2)

[0177] 上記式（1 1)及び式（1 2)中、 及び Rbは、各々独立に、炭素原子、水素原子 、及び酸素原子からなる群より選択される 2つ以上の原子を用いて形成される 2価の 有機基であり、好ましい例としては、置換もしくは無置換の、メチレン基、エチレン基、 プロピレン基、又はブチレン基、エチレンォキシド基、ジエチレンォキシド基、トリェチ レンォキシド基、テトラエチレンォキシド基、ジプロピレンォキシド基、トリプロピレンォ キシド基、テトラプロピレンォキシド基が挙げられる。 [0177] In the above formulas (11) and (12), and Rb are each independently two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. Preferred examples of the divalent organic group to be formed include substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group, ethylene oxide group, diethylene oxide group, triethylene oxide group, tetra Examples include an ethylene oxide group, a dipropylene oxide group, a tripropylene oxide group, and a tetrapropylene oxide group.

[0178] また、 L2は、直鎖、分岐、若しくは環状のアルキレン基、芳香族基、又はこれらを組 み合わせた基であることが好まし!/、。該アルキレン基と芳香族基とを組み合わせた基 は、更に、エーテル基、エステル基、アミド基、ウレタン基、ウレァ基を介していてもよ い。中でも、 L2は総炭素数が 1〜； 15であることが好ましぐ特に無置換であることが好 ましい。なお、ここで、 L2の総炭素数とは、 L2で表される置換もしくは無置換の二価の 有機基に含まれる総炭素原子数を意味する。 [0178] In addition, L 2 represents a linear, branched, or cyclic alkylene group, an aromatic group, or a combination thereof. It's preferable to have a combined group! / The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L 2 preferably has a total carbon number of 1 to 15 and is particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L 2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 2.

具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、フエ二レン基 、及びこれらの基が、メトキシ基、ヒドロキシ基、塩素原子、臭素原子、フッ素原子等で 置換されたもの、更には、これらを組み合わせた基が挙げられる。  Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, etc. Includes a combination of these.

[0179] 本発明の二トリル基含有重合性ポリマーの好ましい例としては、前記式（1)で表さ れるユニットが、下記式（3)で表されるユニットであるものが挙げられる。  [0179] Preferable examples of the nitrile group-containing polymerizable polymer of the present invention include those in which the unit represented by the formula (1) is a unit represented by the following formula (3).

[0180] [化 18]  [0180] [Chemical 18]

。

Figure imgf000057_0001
R2 .
Figure imgf000057_0001
R 2

式 （3 )  Formula (3)

[0181] 上記式（3)中、 R1及び R2は、各々独立に、水素原子、又は置換もしくは無置換の アルキル基を表し、 Zは、単結合、置換もしくは無置換の二価の有機基、エステル基 、アミド基、又はエーテル基を表し、 Wは、酸素原子、又は NR (Rは、水素原子、又は アルキル基を表し、好ましくは、水素原子、又は炭素数 1〜5の無置換のアルキル基 である。）を表し、 L1は、置換もしくは無置換の二価の有機基を表す。 [0181] In the above formula (3), R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond, a substituted or unsubstituted divalent organic group. Group represents an ester group, an amide group, or an ether group, W represents an oxygen atom, or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom, or an unsubstituted one having 1 to 5 carbon atoms. L 1 represents a substituted or unsubstituted divalent organic group.

[0182] 式（3)における R1及び R2は、前記式（1)における R1及び R2と同義であり、好ましい 例も同様である。 R 1 and R 2 in [0182] Equation (3), the formula (1) have the same meanings as R 1 and R 2 in, and so are the preferable examples.

[0183] 式（3)における Zは、前記式（1)における Zと同義であり、好ましい例も同様である。 また、式（3)における L1も、前記式（1)における L1と同義であり、好ましい例も同様 である。 [0183] Z in the formula (3) has the same meaning as Z in the formula (1), and preferred examples thereof are also the same. Further, L 1 in the formula (3) has the same meaning as L 1 in the formula (1), and preferred examples thereof are also the same.

[0184] 本発明の二トリル基含有重合性ポリマーとしては、前記式（3)で表されるユニットが [0184] The nitrile group-containing polymerizable polymer of the present invention includes a unit represented by the formula (3).

、下記式 (4)で表されるユニットであることが好まし!/、。 It is preferable that the unit is represented by the following formula (4)! /.

[0185] [化 19] [0185] [Chemical 19]

Figure imgf000058_0001
式 （4》
Figure imgf000058_0001
Formula (4)

[0186] 式 (4)中、 R1及び R2は、各々独立に、水素原子、又は置換もしくは無置換のアルキ ル基を表し、 V及び Wは、各々独立に、酸素原子、又は NR(Rは、水素原子、又はァ ルキル基を表し、好ましくは、水素原子、又は炭素数 1〜5の無置換のアルキル基で ある。）を表し、 L1は、置換もしくは無置換の二価の有機基を表す。 In formula (4), R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent an oxygen atom or NR ( R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms.), And L 1 represents a substituted or unsubstituted divalent divalent group. Represents an organic group.

[0187] 式 (4)における R1及び R2は、前記式（1)における R1及び R2と同義であり、好ましい 例も同様である。 R 1 and R 2 in [0187] Equation (4), the formula (1) have the same meanings as R 1 and R 2 in, and so are the preferable examples.

[0188] 式 (4)における L1は、前記式（1)における L1と同義であり、好ましい例も同様である[0188] L 1 in the formula (4) has the same meaning as L 1 in the formula (1), and preferred examples thereof are also the same.

〇 Yes

[0189] 前記式（3)及び式 (4)において、 Wは、酸素原子であることが好ましい。  [0189] In the formulas (3) and (4), W is preferably an oxygen atom.

また、前記式（3)及び式（4)において、 L1は、無置換のアルキレン基、或いは、ウレ タン結合又はウレァ結合を有する二価の有機基が好ましぐウレタン結合を有する二 価の有機基がより好ましぐこれら中でも、総炭素数 1〜9であるものが特に好ましい。 In the above formulas (3) and (4), L 1 is a divalent alkylene group, or a divalent group having a urethane bond, preferably a urethane bond or a divalent organic group having a urea bond. Among these, in which organic groups are more preferable, those having 1 to 9 carbon atoms are particularly preferable.

[0190] また、本発明の二トリル基含有重合性ポリマーとしては、前記式（2)で表されるュニ ット力 下記式（5)で表されるユニットであることが好ましい [0190] The nitrile group-containing polymerizable polymer of the present invention includes a unit represented by the above formula (2). It is preferably a unit represented by the following formula (5)

[0191] [化 20] [0191] [Chemical 20]

Figure imgf000059_0001
Figure imgf000059_0001

式 ( 5 )  Formula (5)

[0192] 上記式（5)中、 R5は、水素原子、又は置換もしくは無置換のアルキル基を表し、 U は、酸素原子、又は NR' (ここで R'は、水素原子、又はアルキル基を表し、好ましく は、水素原子、又は炭素数 1 5の無置換のアルキル基である）を表し、を表し、 L2は 、置換もしくは無置換の二価の有機基を表す。 [0192] In the above formula (5), R 5 represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents an oxygen atom, or NR '(where R' is a hydrogen atom or an alkyl group) And preferably represents a hydrogen atom or an unsubstituted alkyl group having 15 carbon atoms, and L 2 represents a substituted or unsubstituted divalent organic group.

[0193] 式（5)における R5は、前記式（1)における R1及び R2と同義であり、水素原子である ことが好ましい。 [0193] R 5 in formula (5) has the same meaning as R 1 and R 2 in formula (1), and is preferably a hydrogen atom.

[0194] また、式（5)における L2は、前記式（1)における L2と同義であり、直鎖、分岐、若しく は環状のアルキレン基、芳香族基、又はこれらを組み合わせた基であることが好まし い。 [0194] Further, L 2 in the formula (5) has the same meaning as L 2 in the formula (1), and a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these Is preferred.

特に、式（5)においては、 L2中のシァノ基との連結部位力 直鎖、分岐、若しくは環 状のアルキレン基を有する二価の有機基であるものが挙げられ、中でも、この二価の 有機基が総炭素数 1〜； 10であるものがより好ましい。 In particular, in the formula (5), there can be mentioned those which are divalent organic groups having a linear, branched, or cyclic alkylene group, and the bonding site strength with the cyan group in L 2. It is more preferable that the organic group has a total carbon number of 1 to 10;

また、別の好ましい態様としては、式（5)における L2中のシァノ基との連結部位が、 芳香族基を有する二価の有機基であるものが挙げられ、中でも、該二価の有機基が 、総炭素数 6〜； 15であるものがより好ましい。 Another preferred embodiment is one in which the linking site with the cyan group in L 2 in formula (5) is a divalent organic group having an aromatic group. More preferably, the group has a total carbon number of 6 to 15;

[0195] 本発明の二トリル基含有重合性ポリマーは、前記式（1)〜式（5)で表されるユニット を含んで構成されるものであり、重合性基と二トリル基とを側鎖に有するポリマーであ この二トリル基含有重合性ポリマーは、例えば、以下のように合成することができる。 [0195] The nitrile group-containing polymerizable polymer of the present invention comprises units represented by the above formulas (1) to (5), and has a polymerizable group and a nitrile group side by side. Is a polymer in the chain This nitrile group-containing polymerizable polymer can be synthesized, for example, as follows.

[0196] 本発明の二トリル基含有重合性ポリマーを合成する際の重合反応の種類としては、 ラジカル重合、カチオン重合、ァニオン重合が挙げられる。反応制御の観点から、ラ ジカル重合、カチオン重合を用いることが好ましい。 [0196] Examples of the polymerization reaction when synthesizing the nitrile group-containing polymerizable polymer of the present invention include radical polymerization, cationic polymerization, and anion polymerization. From the viewpoint of reaction control, it is preferable to use radical polymerization or cationic polymerization.

本発明の二トリル基含有重合性ポリマーは、 1)ポリマー主鎖を形成する重合形態と 側鎖に導入される重合性基の重合形態とが異なる場合と、 2)ポリマー主鎖を形成す る重合形態と側鎖に導入される重合性基の重合形態とが同一の場合と、でその合成 方法が異なる。  The nitrile group-containing polymerizable polymer of the present invention includes: 1) the case where the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain, and 2) the formation of the polymer main chain. The synthesis method differs depending on whether the polymerization form is the same as the polymerization form of the polymerizable group introduced into the side chain.

[0197] 1)ポリマー主鎖を形成する重合形態と側鎖に導入される重合性基の重合形態が異 なる場合  [0197] 1) When the polymerization form of the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain

ポリマー主鎖を形成する重合形態と側鎖に導入される重合性基の重合形態が異な る場合は、 1 1)ポリマー主鎖形成がカチオン重合で行われ、側鎖に導入される重 合性基の重合形態がラジカル重合である態様と、 1 2)ポリマー主鎖形成がラジカ ル重合で行われ、側鎖に導入される重合性基の重合形態がカチオン重合である態 様と、がある。  When the polymerization form that forms the polymer main chain and the polymerization form of the polymerizable group that is introduced into the side chain are different: 1 1) Polymerization that is carried out by cationic polymerization and introduced into the side chain There are embodiments in which the polymerization form of the group is radical polymerization, and 1 2) the formation of the polymer main chain is carried out by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization. .

[0198] 1 1)ポリマー主鎖形成がカチオン重合で行われ、側鎖に導入される重合性基の重 合形態がラジカル重合である態様  [0198] 1 1) A mode in which the polymer main chain is formed by cationic polymerization, and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization.

本発明において、ポリマー主鎖形成がカチオン重合で行われ、側鎖に導入される 重合性基の重合形態がラジカル重合である態様で用いられるモノマーとしては、以 下の化合物が挙げられる。  In the present invention, examples of the monomer used in an embodiment in which the polymer main chain is formed by cationic polymerization and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization include the following compounds.

[0199] ·重合性基含有ユニットを形成するために用いられるモノマー  [0199] · Monomer used to form polymerizable group-containing unit

本態様に用いられる重合性基含有ユニットを形成するために用いられるモノマーと しては、ビュル (メタ）アタリレート、ァリル (メタ）アタリレート、 4— (メタ）アタリロイルブタ ンビュルエーテル、 2 （メタ）アタリロイルェタンビュルエーテル、 3 （メタ）アタリロイ ノレプロノ ンビニノレエーテノレ、 (メタ)アタリロイ口キシジエチレングリコーノレビニノレエー テノレ、 （メタ）アタリロイロキシトリエチレングリコーノレビニノレエーテノレ、 （メタ）アタリロイノレ 1stテルピオネール、 1— (メタ）アタリロイ口キシ一 2—メチル 2—プロペン、 1— (メタ )アタリロイ口キシ一 3 メチル 3 ブテン、 3 メチレン一 2— (メタ）アタリロイロキシ アタリレート、 2—（ブロモメチル）アクリル酸ビュル、 2 - ァリル等が挙げられる。 Monomers used to form the polymerizable group-containing unit used in the present embodiment include bur (meth) acrylate, allyl (meth) acrylate, 4- (meth) attaroyl butyl butyl ether, 2 (Meth) Ataliloyl tert-butyl ether, 3 (Meth) Atalloy Rolepronovininoreatenore, (Meth) Atalloyroxydiethyleneglycolenorevininoreate Tenole, (Meth) Atalloyrooxytriethyleneglycololevininoateoret, (Meth) Atariroinole 1st terpioneer, 1— (Meth) Atariloy oxyl 2-methyl 2-propene, 1— (Meth) Atalloy oxynoxy 3 Methyl 3 butene, 3 Methylene -1- 2-(Meth) Atarileurooxy Atalylate, 2- (bromomethyl) acrylic acid butyl, 2-aryl and the like.

[0200] '二トリル基含有ユニットを形成するために用いられるモノマー  [0200] 'Monomers used to form nitrile group-containing units

本態様に用いられる二トリル基含有ユニットを形成するために用いられるモノマーと しては、 2 シァノエチルビュルエーテル、シァノメチルビュルエーテル、 3 シァノプ 口ピルビュルエーテル、 4—シァノブチルビュルエーテル、 1— (p シァノフエノキシ） 2—ビニロキシーェタン、 1一（o シァノフエノキシ）ー2—ビニロキシーェタン、 1 (m シァノフエノキシ）一 2 ビニロキシーェタン、 1一 （p シァノフエノキシ）一 3— ビニロキシ一プロパン、 1— (p シァノフエノキシ） 4—ビニロキシ一ブタン、 o シ ァノベンジルビュルエーテル、 m シァノベンジルビュルエーテル、 p シァノベンジ ルビニルエーテル、ァリルシアニド、ァリルシアノ酢酸や、以下の化合物等が挙げら れる。  Monomers used to form the nitrile group-containing unit used in this embodiment include 2 cyanoethyl butyl ether, cyanomethyl butyl ether, 3 cyanopropyl pyrulb ether, and 4- cyanobutyl butyl ether. 1— (p-Cyanophenyl) 2—Vinyloxyethane, 1—1 (o-Cyanofenoxy) —2—Vinyloxyethane, 1 (m-Cyanofenoxy) -1 2 Vinyloxy-ethane, 1—1 (P-Cyanophenyl) 1—3—Vinyloxy 1 propane, 1- (p cyanophenoxy) 4 -vinyloxy monobutane, o cyanobenzyl butyl ether, m cyano benzyl butyl ether, p cyano benzyl vinyl ether, allylic cyanide, allyl cyanoacetic acid, and the following compounds.

[0201] [化 21]  [0201] [Chemical 21]

Figure imgf000061_0001
Figure imgf000061_0001

CN

Figure imgf000061_0002
CN
Figure imgf000061_0002

[0202] 重合方法としては、実験化学講座「高分子化学」 2章 4 (ρ74)に記載の方法や、「 高分子合成の実験方法」大津隆行著 7章 (ρ195)に記載の一般的なカチオン重合 法が使用できる。なお、カチオン重合において用いることができる開始剤の例として は、プロトン酸、ハロゲン化金属、有機金属化合物、有機塩、金属酸化物及び固体 酸、ハロゲンが挙げられる。この中でも、ハロゲン化金属と有機金属化合物が、活性 が大きく高分子量が合成可能な開始剤であることから好ましい。 [0202] Polymerization methods include those described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 4 (ρ74), and “Experimental Methods for Polymer Synthesis” written by Takatsu Otsu, Chapter 7 (ρ195). Cationic polymerization can be used. Examples of initiators that can be used in cationic polymerization include proton acids, metal halides, organometallic compounds, organic salts, metal oxides, solid acids, and halogens. Of these, metal halides and organometallic compounds are active. Is preferable because it is a large initiator having a high molecular weight.

具体例としては、 3フッ化ホウ素、 3塩化ホウ素、塩化アルミ、臭化アルミ、四塩化チ タン、四塩化スズ、臭化スズ、 5フッ化リン、塩化アンチモン、塩化モリブデン、塩化タ ングステン、塩化鉄、ジクロロェチルアルミニウム、クロロジェチルアルミニウム、ジクロ ロメチルアルミニウム、クロロジメチルアルミニウム、トリメチルアルミニウム、トリメチル 亜鉛、メチルダリニアが挙げられる。  Specific examples include boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, tin bromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, and chloride. Examples include iron, dichloroethylaluminum, chlorojetylaluminum, dichloromethylaluminum, chlorodimethylaluminum, trimethylaluminum, trimethylzinc, and methyldarinia.

[0203] 1 2)ポリマー主鎖形成がラジカル重合で行われ、側鎖に導入される重合性基の重 合形態がカチオン重合である態様 [0203] 1 2) An embodiment in which the polymer main chain is formed by radical polymerization, and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

本発明において、ポリマー主鎖形成がラジカル重合で行われ、側鎖に導入される 重合性基の重合形態がカチオン重合である態様用いられるモノマーとしては、以下 の化合物が挙げられる。  In the present invention, the following compounds may be used as the monomer used in an embodiment in which the polymer main chain is formed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

[0204] ·重合性基含有ユニットを形成するために用いられるモノマー [0204] · Monomer used to form polymerizable group-containing unit

上記 1 1)の態様で挙げた重合性基含有ユニット形成するために用いられるモノ マーと同じものを用いることができる。  The same monomers as those used for forming the polymerizable group-containing unit mentioned in the above aspect 11) can be used.

[0205] ·二トリル基含有ユニットを形成するために用いられるモノマー [0205] Monomers used to form nitrile group-containing units

本態様に用いられる二トリル基含有ユニットを形成するために用いられるモノマーの 例としては、シァノメチル (メタ）アタリレート、 2 シァノエチル (メタ）アタリレート、 3 - チル（メタ）アタリレート、 4ーシァノブチル（メタ）アタリレート、 5—シァノペンチル（メタ） アタリレート、 6—シァノへキシル（メタ）アタリレート、 7—シァノへキシル（メタ）アタリレ ート、 8 シァノへキシル（メタ）アタリレート、 2 シァノエチルー（3 （ブロモメチル） アクリルレート）、 2 シァノエチルー（3—(ヒドロキシメチル）アクリルレート）、 p シァ ノフエニル（メタ）アタリレート、 o シァノフエニル（メタ）アタリレート、 m シァノフエ二 ノレ（メタ）アタリレート、 5 （メタ）アタリロイルー 2 カルボ二トリローノルボルネン、 6— (メタ）アタリロイル― 2—カルボ二トリ口―ノルボルネン、 1―シァノ— 1— (メタ）アタリ口 ィル一シクロへキサン、 1 , 1—ジメチルー 1—シァノ （メタ）アタリレート、 1—ジメチ ルー 1ーェチルー 1ーシァノー (メタ）アタリレート、 o シァノベンジル（メタ）アタリレー シァノシクロへプチルアタリレート、 2 シァノフエニルアタリレート、 3 シァノフエニル アタリレート、シァノ酢酸ビュル、 1 シァノ 1ーシクロプロパンカルボン酸ビュル、シ ァノ酢酸ァリル、 1 シァノ 1ーシクロプロパンカルボン酸ァリル、 N, N—ジシァノメ チル (メタ）アクリルアミド、 N シァノフエニル (メタ）アクリルアミド、ァリルシアノメチル エーテル、ァリルー o—シァノエチルエーテル、ァリルー m シァノベンジルエーテル 、ァリル p シァノベンジルエーテルなどが挙げられる。 Examples of monomers used to form the nitrile group-containing unit used in this embodiment include cyanomethyl (meth) acrylate, 2- cyanoethyl (meth) acrylate, 3- til (meth) acrylate, 4-cyano butyl ( (Meth) atarylate, 5—cyanopentyl (meth) atallylate, 6—cyanhexyl (meth) acrylate, 7—cyanhexyl (meth) acrylate, 8 cyanhexyl (meth) acrylate, 2 cyanoethyl ( 3 (bromomethyl) acrylate), 2 cyanoethyl (3- (hydroxymethyl) acrylate), p cyanophenyl (meth) acrylate, o cyanophenyl (meth) acrylate, m cyanophenyl (meth) acrylate, 5 ( Meta) Atari Roy Roux 2 Carbonitorilonorbornene, 6— (Meth) Atarylloyl— 2-Carbonitol-norbornene, 1-Cyanone— 1— (Meth) Atariyl-cyclohexane, 1, 1-Dimethyl-1-ciano (meth) acrylate, 1— Dimethyru 1-Etilu 1-Cyanano (meth) attalylate, o Cyanobenzyl (meth) attalay Cyancycloheptyl acrylate, 2 cyanophenyl acrylate, 3 cyanophenyl acrylate, cyan acetate butyl, 1 cyano 1-cyclopropanecarboxylate butyl, cyano acetate allyl, 1 cyano 1-cyclopropane carboxylic acid, N, N-disyanmethyl (meth) acrylamide, N-cyanophenyl (meth) acrylamide, allyl cyanomethyl ether, allylo o- cyanoethyl ether, allylo m cyanobenzyl ether, allyl p cyanobenzyl ether and the like.

また、上記モノマーの水素の一部を、ヒドロキシル基、アルコキシ基、ハロゲン、シァ ノ基などで置換した構造を持つモノマーも使用可能である。  A monomer having a structure in which a part of hydrogen of the monomer is substituted with a hydroxyl group, an alkoxy group, a halogen, a cyan group, or the like can also be used.

[0206] 重合方法としては、実験化学講座「高分子化学」 2章 2 (p34)に記載の方法や、「 高分子合成の実験方法」大津隆行著 5章 (pl25)に記載の一般的なラジカル重合 法が使用できる。なお、ラジカル重合の開始剤には、 100°C以上の加熱が必要な高 温開始剤、 40〜100°Cの加熱で開始する通常開始剤、極低温で開始するレドックス 開始剤などが知られているが、開始剤の安定性、重合反応のハンドリングのし易さか ら、通常開始剤が好ましい。 [0206] Polymerization methods include those described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu, Chapter 5 (pl25). A radical polymerization method can be used. Examples of radical polymerization initiators include high-temperature initiators that require heating of 100 ° C or higher, normal initiators that start with heating at 40 to 100 ° C, and redox initiators that start at extremely low temperatures. However, an initiator is usually preferred because of the stability of the initiator and ease of handling of the polymerization reaction.

通常開始剤の例としては、過酸化べンゾィル、過酸化ラウロイル、ペルォキソ 2硫酸 塩、ァゾビスイソブチロニトリル、ァゾビル一 2, 4 ジメチルバレロニトリルが挙げられ  Examples of normal initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, and azovir-1,4 dimethylvaleronitrile.

[0207] 2)ポリマー主鎖を形成する重合形態と側鎖に導入される重合性基の重合形態とが 同一の場合 [0207] 2) When the polymerization form of the polymer main chain and the polymerization form of the polymerizable group introduced into the side chain are the same

ポリマー主鎖を形成する重合形態と側鎖に導入される重合性基の重合形態とが同 一の場合は、 2 1)両者がカチオン重合の態様と、 2— 2)両者がラジカル重合であ る態様と、がある。  When the polymerization form that forms the polymer main chain is the same as the polymerization form of the polymerizable group introduced into the side chain, 2 1) both are cationic polymerization modes, and 2-2) both are radical polymerizations. There is a mode.

[0208] 2— 1)両者がカチオン重合の態様 [0208] 2-1) Both are embodiments of cationic polymerization

両者がカチオン重合の態様には、二トリル基を有するモノマーとして、前記 1— 1)の 態様で挙げた二トリル基含有ユニット形成するために用いられるモノマーと同じものを 用いること力 Sでさる。  In both embodiments of cationic polymerization, the same monomer as the monomer used for forming the nitrile group-containing unit mentioned in the embodiment 1-1) is used as the monomer having a nitrile group.

なお、重合中のゲル化を防止する観点から、二トリル基を有するポリマーを予め合 成した後、該ポリマーと、カチオン重合性の重合性基を有する化合物（以下、適宜、「 反応性化合物」と称する。）と、を反応させ、側鎖にカチオン重合性の重合性基を導 入する方法を用いることが好ましレヽ。 From the viewpoint of preventing gelation during polymerization, a polymer having a nitrile group is synthesized in advance, and then the polymer and a compound having a cationic polymerizable group (hereinafter referred to as “ This is referred to as a “reactive compound”. And a method in which a cationically polymerizable group is introduced into the side chain.

[0209] なお、二トリル基を有するポリマーは、反応性化合物との反応のために、下記に示 すような反応性基を有することが好ましレ、。 [0209] The polymer having a nitrile group preferably has a reactive group as shown below for reaction with the reactive compound.

また、二トリル基を有するポリマーと反応性化合物とは、以下のような官能基の組み 合わせとなるように、適宜、選択されることが好ましい。  Further, the polymer having a nitrile group and the reactive compound are preferably selected as appropriate so as to have the following combination of functional groups.

具体的な組み合わせの例としては、（ポリマーの反応性基、反応性化合物の官能 基） = (カルボキシル基、カルボキシル基）、 （カルボキシル基、エポキシ基）、 （カルボ キシル基、イソシァネート基）、（カルボキシル基、ハロゲン化ベンジル）、（水酸基、力 ルポキシル基）、（水酸基、エポキシ基）、（水酸基、イソシァネート基）、（水酸基、ハロ ゲン化ベンジル）（イソシァネート基、水酸基）、（イソシァネート基、カルキシル基）等 を挙げること力 Sでさる。  Examples of specific combinations are (polymer reactive group, functional group of reactive compound) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), ( (Carboxyl group, benzyl halide), (hydroxyl group, force propyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group) Group) and so on.

[0210] ここで、反応性化合物の具体例としては、ァリルアルコール、 4ーヒドロキシブタンビ ニノレエーテノレ、 2—ヒドロキシエタンビニノレエーテノレ、 3—ヒドロキシプロパンビニノレエ ーテノレ、ヒドロキシトリエチレングリコーノレビニノレエーテノレ、 1stテノレピオネーノレ、 2—メ チルー 2—プロペノール、 3—メチルー 3—ブテノール、 3—メチレンー2—ヒドロキシ —ノルボルナン、 p— (クロロメチル)スチレンを挙げることができる。  [0210] Here, specific examples of the reactive compound include allylic alcohol, 4-hydroxybutane vinylenoleate, 2-hydroxyethanevininoreatenore, 3-hydroxypropane vinylenoleate, hydroxytriethyleneglycolenolebi. Mention may be made of ninoleatenore, 1st tenolepioneore, 2-methyl-2-propenol, 3-methyl-3-butenol, 3-methylene-2-hydroxy-norbornane, p- (chloromethyl) styrene.

[0211] 2— 2)両者がラジカル重合である態様  [0211] 2-2) A mode in which both are radical polymerization

両者がラジカル重合である態様では、合成方法としては、 i)二トリル基を有するモノ マーと重合性基を有するモノマーとを共重合する方法、 ii)二トリル基を有するモノマ 一と二重結合前駆体を有するモノマーとを共重合させ、次に塩基などの処理により二 重結合を導入する方法、 iii)二トリル基を有するポリマーと重合性基を有するモノマー とを反応させ、二重結合を導入 (重合性基を導入する)方法が挙げられる。合成適性 の観点から好ましいのは、 ii)二トリル基を有するモノマーと二重結合前駆体を有する モノマーとを共重合させ、次に塩基などの処理により二重結合を導入する方法、 iii) 二トリル基を有するポリマーと重合性基を有するモノマーとを反応させ、重合性基を導 入する方法である。  In an embodiment in which both are radical polymerization, synthesis methods include i) a method of copolymerizing a monomer having a nitrile group and a monomer having a polymerizable group, and ii) a monomer having a nitrile group and a double bond. A method in which a monomer having a precursor is copolymerized and then a double bond is introduced by treatment with a base or the like; iii) a polymer having a nitrile group and a monomer having a polymerizable group are reacted to form a double bond. An introduction method (introducing a polymerizable group) can be mentioned. From the viewpoint of synthesis suitability, ii) a method in which a monomer having a nitrile group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base, etc. In this method, a polymer having a tolyl group is reacted with a monomer having a polymerizable group to introduce a polymerizable group.

[0212] 前記 i)の合成方法で用いられる重合性基を有するモノマーとしては、ァリル (メタ)ァ タリレートや、以下の化合物などが挙げられる。 [0212] Examples of the monomer having a polymerizable group used in the synthesis method i) include a aryl (meth) Examples include talirate and the following compounds.

[0213] [化 22]  [0213] [Chemical 22]

Figure imgf000065_0001
Figure imgf000065_0001

[0214] 前記 ii)の合成方法で用いられる二重結合前駆体を有するモノマーとしては、下記 式 ωで表される化合物などが挙げられる。 [0214] Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula ω.

[0215] [化 23]  [0215] [Chemical 23]

Figure imgf000065_0002
Figure imgf000065_0002

[0216] 上記式 (a)中、 Aは重合性基を有する有機団、 R1〜！ Tは、各々独立に、水素原子 又は 1価の有機基、 B及び Cは脱離反応により除去される脱離基であり、ここでいう脱 離反応とは、塩基の作用により Cが引き抜かれ、 Bが脱離するものである。 Bはァニォ ンとして、 Cはカチオンとして脱離するものが好まし!/、。 [0216] In the above formula (a), Yukidan A is having a polymerizable group, R 1 ~! T is independently a hydrogen atom or a monovalent organic group, B and C are leaving groups that are removed by a leaving reaction, and the term “separating reaction” here refers to C being extracted by the action of a base. , B is desorbed. B is preferred as anion and C as a cation! /.

式 (a)で表される化合物としては、具体的には以下の化合物を挙げることができる。  Specific examples of the compound represented by the formula (a) include the following compounds.

[0217] [化 24] [8IZ0] [0217] [Chemical 24] [8IZ0]

Figure imgf000066_0001
Figure imgf000066_0001

StSOLO/LOOZdT/lDd 99 S 0S0/800Z: OAV

Figure imgf000067_0001
StSOLO / LOOZdT / lDd 99 S 0S0 / 800Z: OAV
Figure imgf000067_0001

[0219] また、前記 [0219] In addition,

下記に示すように、 B、 Cで表される脱離基を脱離反応により除去する方法、つまり、 塩基の作用により Cを引き抜き、 Bが脱離する反応を使用する。  As shown below, a method is used in which the leaving groups represented by B and C are removed by an elimination reaction, that is, a reaction in which B is eliminated by extracting C by the action of a base.

[0220] [化 26]  [0220] [Chemical 26]

Figure imgf000067_0002
Figure imgf000067_0002

[0221] 上記の脱離反応において用いられる塩基の好ましい例としては、アルカリ金属類の 水素化物、水酸化物又は炭酸塩、有機アミ化合物、金属アルコキシド化合物が挙げ られる。アルカリ金属類の水素化物、水酸化物、又は炭酸塩の好ましい例としては、 水素化ナトリウム、水素化カルシウム、水素化カリウム、水酸化ナトリウム、水酸化カリ ゥム、水酸化カルシウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素 ナトリウムなどが挙げられる。有機アミン化合物の好ましい例としては、トリメチルァミン 、卜リエチノレ ミン、ジェチノレメチノレ ミン、卜リフ"チノレ ミン、卜リイソフ"チノレ ミン、卜リ へキシルァミン、トリオクチノレアミン、 N, N ジメチルシクロへキシルァミン、 N, N— ジェチノレシクロへキシノレアミン、 N メチノレジシクロへキシノレアミン、 N ェチノレジシク 口へキシルァミン、ピロリジン、 1 メチルピロリジン、 2, 5—ジメチルピロリジン、ピペリ ジン、 1ーメチノレビペリジン、 2, 2, 6, 6—テトラメチノレビペリジン、ピぺラジン、 1 , 4 ジメチノレビペラジン、キヌタリジン、 1 , 4ージァザビシクロ [2, 2, 2] オクタン、へキ サメチレンテトラミン、モノレホリン、 4ーメチノレモノレホリン、ピリジン、ピコリン、 4 ジメチ ノレアミノビリジン、ノレチジン、 1 , 8 ジァザビシクロ〔5, 4, 0〕 7 ゥンデセン（DBU )、 N, N'—ジシクロへキシルカルポジイミド（DCC)、ジイソプロピルェチルァミン、 S chiff塩基などが挙げられる。金属アルコキシド化合物の好ましい例としては、ナトリウ ムメトキシド、ナトリウムェトキシド、カリウム t ブトキシドなどが挙げられる。これらの塩 基は、 1種或いは 2種以上の混合であってもよい。 [0221] Preferable examples of the base used in the above elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, carbonate Sodium, potassium hydrogen carbonate, sodium hydrogen carbonate, etc. are mentioned. Preferable examples of the organic amine compound include trimethylamine, rietinolemin, jetinoremethinolemine, 卜 lif チ noremine, 卜 liisof チ nolemine, 卜 hexylamine, trioctinoleamine, N, N dimethyl Cyclohexylamine, N, N- ethynolecyclohexenoleamine, N methinoresincyclohexenoleamine, N ethenoresic mouth hexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methinoleviperidine, 2, 2 , 6, 6—tetramethinorebiperidine, piperazine, 1, 4 Dimethinoleviperazine, quinutaridin, 1,4-diazabicyclo [2, 2, 2] octane, hexamethylenetetramine, monoreforin, 4-methinoremonoreforin, pyridine, picoline, 4 dimethylenoreaminoviridine, noretidine, 1, 8 diazabicyclo [5, 4, 0] 7undecene (DBU), N, N'-dicyclohexyl carpositimide (DCC), diisopropylethylamine, Schiff base and the like. Preferred examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These base groups may be one kind or a mixture of two or more kinds.

[0222] また、前記脱離反応において、塩基を付与（添加）する際に用いられる溶媒の例と しては、エチレンジクロリド、シクロへキサノン、メチルェチルケトン、アセトン、メタノー ノレ、エタノーノレ、プロノ ノーノレ、ブタノーノレ、エチレングリコーノレモノメチノレエーテノレ、 エチレングリコーノレモノェチノレエーテノレ、 2—メトキシェチノレアセテート、 1ーメトキシ 2—プロパノール、 1ーメトキシー2—プロピルアセテート、 N, N ジメチルホルム アミド、 N, N ジメチルァセトアミド、ジメチルスルホキシド、トルエン、酢酸ェチル、乳 酸メチル、乳酸ェチル、水などが挙げられる。これらの溶媒は単独或いは 2種以上混 合してもよい。 [0222] Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, prono. Nonole, Butanol, Ethyleneglycololemonomethinoatenore, Ethyleneglycolenomonoethylenoatere, 2-methoxyethinoreacetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N dimethylformamide N, N dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

[0223] 使用される塩基の量は、化合物中の特定官能基 (B、 Cで表される脱離基）の量に 対して、当量以下であってもよぐまた、当量以上であってもよい。また、過剰の塩基 を使用した場合、脱離反応後、余剰の塩基を除去する目的で酸などを添加すること も好ましい形態である。  [0223] The amount of the base used may be less than or equal to the amount of the specific functional group (leaving group represented by B or C) in the compound. Also good. In addition, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

[0224] 前記 iii)の合成方法において用いられる二トリル基を有するポリマーは、上記 1 2) の態様で挙げた二トリル基含有ユニット形成するために用いられるモノマーと、二重 結合導入のための反応性基を有するモノマーと、をラジカル重合することにより合成 される。  [0224] The polymer having a nitrile group used in the synthesis method of iii) includes a monomer used for forming the nitrile group-containing unit mentioned in the above embodiment 1 2) and a double bond introduction. It is synthesized by radical polymerization of a monomer having a reactive group.

二重結合導入のための反応性基を有するモノマーの例としては、反応性基として力 ルポキシル基、水酸基、エポキシ基、又はイソシァネート基を有するモノマーが挙げ られる。  Examples of the monomer having a reactive group for introducing a double bond include a monomer having a reactive carboxyl group, a hydroxyl group, an epoxy group, or an isocyanate group as a reactive group.

[0225] カルボキシル基含有のモノマーの例としては、（メタ）アクリル酸、ィタコン酸、安息香 酸ビュル；東亞合成製のァロニタス M— 5300、 M— 5400、 M— 5600 (全て商品名 )；三菱レーシヨン製のアクリルエステル PA、 HH (全て商品名）；共栄社化学製のライ トアタリレート HOA—HH (全て商品名）；中村化学製の NKエステル SA、 A— SA( 全て商品名）などが挙げられる。 [0225] Examples of carboxyl group-containing monomers include (meth) acrylic acid, itaconic acid, benzoic acid bur; Alonitas M-5300, M-5400, M-5600 manufactured by Toagosei (all trade names) ); Mitsubishi Rayon Acrylic Esters PA, HH (all trade names); Kyoeisha Chemical Light Atylate HOA—HH (all trade names); Nakamura Chemical NK Esters SA, A— SA (all trade names) Etc.

水酸基含有のモノマーの例としては、 2 ヒドロキシェチル（メタ）アタリレート、 4 ヒ ドロキシブチル（メタ）アタリレート、 2—ヒドロキシプロピル（メタ）アタリレート、 2—ヒドロ キシブチル（メタ）アタリレート、 1 - (メタ）アタリロイル一 3—ヒドロキシ一ァダマンタン、 ヒドロキシメチル (メタ）アクリルアミド、 2- (ヒドロキシメチル） （メタ）アタリレート、 2- (ヒドロキシメチル） （メタ）アタリレートのメチルエステル、 3 クロロー 2 ヒドロキシ プロピル（メタ）アタリレート、 3, 5—ジヒドロキシペンチル（メタ）アタリレート、 1ーヒドロ キシメチルー 4 （メタ）アタリロイルメチルーシクロへキサン、 2 ヒドロキシー3 フエ  Examples of hydroxyl group-containing monomers include 2 hydroxyethyl (meth) acrylate, 4 hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (Meth) Atarylloyl 3-hydroxy-1-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl) (meth) atalylate, 2- (hydroxymethyl) methyl ester of (meth) atalylate, 3 chloro-2-hydroxypropyl (Meth) Athalylate, 3,5-Dihydroxypentyl (Meth) Atalylate, 1-Hydroxymethyl-4 (Meth) Ataliloylmethyl-cyclohexane, 2 Hydroxy-3 Hue

2 アタリロイロキシェチルー 2—ヒドロキシェチルフタル酸、 1ーメチルー 2—アタリ口 ドロキシー 3—クロ口プロピルフタル酸；東亞合成（株）製のァロニタス M— 554、 M— 154、 M— 555、 M— 155、 M— 158 (全て商品名）；日本油脂（株）製のブレンマー PE— 200、 PE— 350、 PP— 500、 PP— 800、 PP— 1000、 70PEP— 350B、 55P ET800 (全て商品名）；及び、以下の構造を有するラタトン変性アタリレートが挙げら れる。 2 Atalloylokischetil 2-hydroxyethyl phthalic acid, 1-methyl 2-Atari mouth droxy 3-chloro mouth propyl phthalic acid; Alonitas M-554, M-154, M-555, M, manufactured by Toagosei Co., Ltd. — 155, M— 158 (all trade names); Bremmer PE—200, PE—350, PP—500, PP—800, PP—1000, 70PEP—350B, 55P ET800 (all trade names) ); And Rataton-modified attalylate having the following structure.

CH =CRCOOCH CH [OC ( = 0) C H ] OH  CH = CRCOOCH CH [OC (= 0) C H] OH

2 2 2 5 10 n  2 2 2 5 10 n

(R=H又はメチル基、 n= l〜5)  (R = H or methyl group, n = l to 5)

[0226] エポキシ基を有するモノマーの例としては、グリシジル（メタ）アタリレート、ダイセル 化学製のサイクロマー A、 M (共に商品名）などが挙げられる。 [0226] Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, Cyclomers A and M (both trade names) manufactured by Daicel Chemical Industries, and the like.

イソシァネート基を有するモノマーの例としては、昭和電工製の力レンズ AOI、 MOI (共に商品名）が挙げられる。  Examples of monomers having an isocyanate group include power lenses AOI and MOI (both trade names) manufactured by Showa Denko.

なお、 iii)の合成方法において用いられる二トリル基を有するポリマーは、更に第 3 の共重合成分を含んでレ、てもよレ、。  The polymer having a nitrile group used in the synthesis method iii) may further contain a third copolymer component.

[0227] 前記 iii)の合成方法にお!/、て、二トリル基を有するポリマーと反応させる重合性基を 有するモノマーは、二トリル基を有するポリマー中の反応性基の種類によって異なる。 以下の組合せの官能基を有するモノマーを使用することができる。 [0227] In the synthesis method of iii) above, the monomer having a polymerizable group to be reacted with the polymer having a nitrile group varies depending on the kind of the reactive group in the polymer having a nitrile group. Monomers having the following combinations of functional groups can be used.

即ち、（ポリマーの反応性基、モノマーの官能基） = (カルボキシル基、カルボキシ ル基）、（カルボキシル基、エポキシ基）、（カルボキシル基、イソシァネート基）、（カル ボキシル基、ハロゲン化べンジル）、（水酸基、カルボキシル基）、（水酸基、エポキシ 基）、（水酸基、イソシァネート基）、（水酸基、ハロゲン化ベンジル）（イソシァネート基 、水酸基）、（イソシァネート基、カルボキシル基）、（エポキシ基、カルボキシル基）等 を挙げること力 Sでさる。  That is, (polymer reactive group, monomer functional group) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide) , (Hydroxyl group, carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, benzyl halide) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), (epoxy group, carboxyl group) ) Etc. Power S.

具体例としては以下のモノマーが挙げられる。  Specific examples include the following monomers.

[0228] [化 27] [0228] [Chemical 27]

Figure imgf000070_0001
Figure imgf000070_0001

[0229] 本発明の二トリル基含有重合性ポリマーにおいて、前記式（1)、式（3)、又は式 (4) における L1がウレタン結合を有する二価の有機基である構造の場合には、以下に示 す合成方法 (本発明のポリマーの合成方法）で合成することが好まし!/、。 [0229] In the nitrile group-containing polymerizable polymer of the present invention, when L 1 in the formula (1), formula (3), or formula (4) is a divalent organic group having a urethane bond, Is preferably synthesized by the synthesis method shown below (method for synthesizing the polymer of the present invention)!

本発明のポリマーの合成方法は、少なくとも溶媒中で、側鎖にヒドロキシル基を有 するポリマー、及び、イソシァネート基と重合性基とを有する化合物を用い、該ヒドロ キシル基に該イソシァネート基を付加させることにより L1中のウレタン結合を形成する ことを特徴とする。 In the method for synthesizing the polymer of the present invention, at least in a solvent, a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group are used, and the isocyanate group is added to the hydroxyl group. and forming a urethane bond in L 1 by.

[0230] ここで、本発明のポリマーの合成方法に用いられる側鎖にヒドロキシル基を有する ポリマーの好ましい例としては、上記 1— 2)の態様で挙げた二トリル基含有ユニット形 成するために用いられるモノマーと、以下に示す挙げるヒドロキシル基含有 (メタ）ァク リレートと、の共重合体が挙げられる。 [0230] Here, as a preferable example of the polymer having a hydroxyl group in the side chain used in the method for synthesizing the polymer of the present invention, the unit type containing nitrile group described in the above embodiment 1-2) Examples thereof include copolymers of monomers used for the formation and the following hydroxyl group-containing (meth) acrylates.

ヒドロキシル基含有（メタ）アタリレートの例としては、 2—ヒドロキシェチル (メタ）アタリ ート、 2 ヒドロキシブチル（メタ）アタリレート、 1— (メタ）アタリロイル一 3 ヒドロキシ一 ァダマンタン、ヒドロキシメチノレ (メタ）アタリノレアミド、 2— (ヒドロキシメチル） （メタ）ァ タリレート、 2 （ヒドロキシメチル） （メタ）アタリレートのメチルエステル、 3 クロロー 2 ヒドロキシプロピル（メタ）アタリレート、 3, 5 ジヒドロキシペンチル（メタ）アタリレ ート、 1ーヒドロキシメチノレー 4 （メタ）アタリロイノレメチノレーシクロへキサン、 2—ヒドロ キシー3 フエノキシプロピル（メタ）アタリレート、 1ーメチルー 2—アタリロイロキシプロ ピルフタル酸、 2—アタリロイロキシェチルー 2—ヒドロキシェチルフタル酸、 1ーメチノレ 2—アタリロイロキシェチルー 2—ヒドロキシプロピルフタル酸、 2—アタリロイロキシ ェチルー 2 ヒドロキシ 3 クロ口プロピルフタル酸；東亞合成（株）製のァロニタス M— 554、 M— 154、 M— 555、 M— 155、 M— 158 (全て商品名）；日本油脂（株） 製のブレンマー PE— 200、 PE— 350、 PP— 500、 PP— 800、 PP— 1000、 70PEP 350B、 55PET800 (全て商品名）；及び以下の構造を有するラタトン変性アタリレ ートが挙げられる。  Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (meth) atteroyl 1-3 hydroxy 1 adamantane, hydroxymethinole ( (Meth) atalinoleamide, 2- (hydroxymethyl) (meth) atalylate, 2 (hydroxymethyl) methyl ester of (meth) atalylate, 3 chloro-2 hydroxypropyl (meth) atalylate, 3, 5 dihydroxypentyl (meta) ) Atarylate, 1-Hydroxymethylenole 4 (Meth) Atalylurolemethinole cyclohexane, 2-Hydroxy 3 Phenoxypropyl (meth) acrylate, 1-Methyl-2- Atalylyloxypropyl phthalate, 2 —Atariloylokichetil 2-hydroxyethyl phthalate 1-Methinore 2-Atariloylokichetil 2-hydroxypropylphthalic acid 2-Atarileuoxyethyl 2-hydroxy 3-chloropropyl phthalic acid; Alonitas M-554, M-154, M- from Toagosei Co., Ltd. 555, M-155, M-158 (all trade names); Bremer made by Nippon Oil & Fats Co., Ltd. PE-200, PE-350, PP-500, PP-800, PP-1000, 70PEP 350B, 55PET800 (all products) Name); and Rataton-modified atelate having the following structure.

CH =CRCOOCH CH [OC ( = 0) C H ] OH  CH = CRCOOCH CH [OC (= 0) C H] OH

2 2 2 5 10 n  2 2 2 5 10 n

(R=H又はメチル基、 n= l〜5)  (R = H or methyl group, n = l to 5)

なお、本発明のポリマーの合成方法に用いられる側鎖にヒドロキシル基を有するポ リマーは、更に第 3の共重合成分を含んでいてもよい。  The polymer having a hydroxyl group in the side chain used in the polymer synthesis method of the present invention may further contain a third copolymer component.

上述のような側鎖にヒドロキシル基を有するポリマーの中でも、高分子量体のポリマ 一を合成する観点から、原料として、ヒドロキシ基含有 (メタ）アタリレートを合成する際 に副生する 2官能アタリレートを除去した原料を用いて合成したポリマーを使用するこ とが好ましい。精製の方法としては、蒸留、カラム精製が好ましい。更に好ましくは、 下記（1)〜（4)の工程を順次経ることで得られたヒドロキシル基含有 (メタ）アタリレート を用いて合成されたものであることが好ましレ、。  Among the polymers having a hydroxyl group in the side chain as described above, from the viewpoint of synthesizing a polymer having a high molecular weight, a bifunctional acrylate is produced as a by-product when synthesizing a hydroxy group-containing (meth) acrylate as a raw material. It is preferable to use a polymer synthesized using a raw material from which the water has been removed. As the purification method, distillation and column purification are preferred. More preferably, it is synthesized using a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the following steps (1) to (4).

(1)ヒドロキシノレ基含有 (メタ）アタリレートと、該ヒドロキシノレ基含有 (メタ）アタリレートを 合成する際に副生する 2官能アタリレートと、を含む混合物を、水に溶解する工程(1) Hydroxy group-containing (meth) acrylate and the hydroxy group-containing (meth) acrylate A step of dissolving a mixture containing bifunctional attalylate produced as a by-product during synthesis in water

(2)得られた水溶液に、水と分離する第 1の有機溶剤を加えた後、該第 1の有機溶剤 と前記 2官能アタリレートとを含む層を水層から分離する工程 (2) A step of adding a first organic solvent that separates from water to the obtained aqueous solution, and then separating a layer containing the first organic solvent and the bifunctional acrylate from the aqueous layer.

(3)前記水層に、前記ヒドロキシル基含有 (メタ）アタリレートよりも水溶解性の高!/、化 合物を溶解する工程  (3) A step of dissolving a compound having a higher water solubility than the hydroxyl group-containing (meth) acrylate in the aqueous layer.

(4)前記水層に第 2の有機溶剤を加えて、前記ヒドロキシル基含有 (メタ）アタリレート を抽出した後、濃縮する工程  (4) A step of adding a second organic solvent to the aqueous layer, extracting the hydroxyl group-containing (meth) acrylate, and then concentrating it.

[0232] 前記（1)の工程において用いられる混合物は、ヒドロキシル基含有 (メタ）アタリレー トと、該ヒドロキシル基含有 (メタ）アタリレートを合成する際に副生する不純物である 2 官能アタリレートと、を含んでおり、ヒドロキシル基含有 (メタ）アタリレートの一般的な 市販品に相当する。  [0232] The mixture used in the step (1) is composed of a hydroxyl group-containing (meth) atrelate and a bifunctional atallylate that is an impurity by-produced when the hydroxyl group-containing (meth) acrylate is synthesized. It corresponds to a general commercial product of hydroxyl group-containing (meth) acrylate.

前記（1)の工程では、この市販品（混合物）を水に溶解して、水溶液を得る。  In the step (1), this commercial product (mixture) is dissolved in water to obtain an aqueous solution.

[0233] 前記（2)の工程では、（1)の工程で得られた水溶液に対し、水と分離する第 1の有 機溶剤を加える。ここで用いられる、第 1の有機溶剤の例としては、酢酸ェチル、ジェ チルエーテル、ベンゼン、トルエン等が挙げられる。  [0233] In the step (2), a first organic solvent that separates from water is added to the aqueous solution obtained in the step (1). Examples of the first organic solvent used here include ethyl acetate, jet ether, benzene, toluene and the like.

その後、水溶液 (水層）から、この第 1の有機溶剤と 2官能アタリレートとを含む層（油 層）を分離する。  Thereafter, the layer (oil layer) containing the first organic solvent and the bifunctional acrylate is separated from the aqueous solution (aqueous layer).

[0234] 前記（3)の工程では、（2)の工程で油層と分離された水層に、ヒドロキシル基含有（ メタ）アタリレートよりも水溶解性の高い化合物を溶解する。  In the step (3), a compound having higher water solubility than the hydroxyl group-containing (meth) acrylate is dissolved in the water layer separated from the oil layer in the step (2).

ここで用いられるヒドロキシル基含有 (メタ）アタリレートよりも水溶解性の高!/、化合物 の例としては、塩化ナトリウム、塩化カリウムなどのアルカリ金属塩、硫酸マグネシウム 、硫酸カルシウムなどのアルカリ土類金属塩などの無機塩等が用いられる。  More water-soluble than hydroxyl group-containing (meth) acrylates used here! / Examples of compounds include alkali metal salts such as sodium chloride and potassium chloride, alkaline earth metals such as magnesium sulfate and calcium sulfate An inorganic salt such as a salt is used.

[0235] 前記 (4)の工程では、水層に第 2の有機溶剤を加えて、ヒドロキシル基含有 (メタ）ァ タリレートを抽出した後、濃縮する。 [0235] In the step (4), a second organic solvent is added to the aqueous layer to extract hydroxyl group-containing (meth) atalylate, followed by concentration.

ここで用いられる第 2の有機溶剤の例としては、酢酸ェチル、ジェチルエーテル、 ベンゼン、トルエン等が挙げられる。この第 2の有機溶剤は、前述の第 1の有機溶剤 と同じであってもよいし、異なっていてもよい。  Examples of the second organic solvent used here include ethyl acetate, jetyl ether, benzene, toluene and the like. This second organic solvent may be the same as or different from the first organic solvent described above.

(4)の工程における濃縮には、無水硫酸マグネシウムによる乾燥や、減圧留去等が 用いられる。 Concentration in the step (4) includes drying with anhydrous magnesium sulfate and distillation under reduced pressure. Used.

[0236] 前記（1)〜（4)の工程を順次経ることで得られたヒドロキシル基含有 (メタ）アタリレ ートを含む単離物は、その全質量中に 2官能アタリレートを 0. 1質量％以下の範囲で 含むことが好ましい。つまり、前記（1)〜（4)の工程を経ることで、混合物から不純物 である 2官能アタリレートが除去され、ヒドロキシル基含有 (メタ）アタリレートが精製さ れる。  [0236] An isolate containing a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the steps (1) to (4) described above contains a bifunctional acrylate in a total mass of 0.1. It is preferable to contain in the range below mass%. That is, through the steps (1) to (4), the bifunctional acrylate is removed from the mixture, and the hydroxyl group-containing (meth) acrylate is purified.

2官能アタリレートの含有量のより好ましい範囲は、単離物の全質量中に 0. 05質量 %以下であり、少なければ少なレ、ほどよレ、。  A more preferable range of the content of the bifunctional attalylate is 0.05% by mass or less based on the total mass of the isolate.

このように精製されたヒドロキシル基含有 (メタ）アタリレートを用いることで、不純物 である 2官能アタリレートが重合反応に影響を及ぼし難くなるため、重量平均分子量 力 S20000以上の二トリル基含有重合性ポリマーを合成することができる。  By using such purified hydroxyl group-containing (meth) acrylate, the bifunctional acrylate which is an impurity is less likely to affect the polymerization reaction. Therefore, a nitrile group-containing polymerizable compound having a weight average molecular weight of S20000 or more is required. Polymers can be synthesized.

[0237] 前記（1)の工程において用いられるヒドロキシ基含有 (メタ）アタリレートとしては、前 述の本発明のポリマーの合成方法に用いられる側鎖にヒドロキシル基を有するポリマ 一を合成する際に用いられるヒドロキシル基含有 (メタ）アタリレートとして挙げられたも のを用いること力 Sできる。中でも、イソシァネートへの反応性の観点から、第 1級水酸 基を有するモノマーが好ましぐ更には、ポリマーの単位重量当たりの重合性基比率 を高める観点から、分子量が 100〜250のヒドロキシ基含有 (メタ）アタリレートが好ま しい。 [0237] As the hydroxy group-containing (meth) acrylate used in the step (1), when synthesizing a polymer having a hydroxyl group in the side chain used in the polymer synthesis method of the present invention described above, It is possible to use the ones listed as hydroxyl group-containing (meth) acrylates used. Among these, from the viewpoint of reactivity to isocyanate, a monomer having a primary hydroxyl group is preferred, and from the viewpoint of increasing the ratio of polymerizable groups per unit weight of the polymer, a hydroxy group having a molecular weight of 100 to 250 is preferred. Contained (meth) acrylate is preferred.

[0238] また、本発明のポリマーの合成方法に用いられるイソシァネート基と重合性基とを有 する化合物としては、 2—アタリロイルォキシェチルイソシァネート（商品名：力レンズ A OI、昭和電工（株）製）、 2—メタクリルォキシイソシァネート（商品名：力レンズ MOI、 昭和電工 (株)製)等が挙げられる。  [0238] In addition, as a compound having an isocyanate group and a polymerizable group used in the method for synthesizing a polymer according to the present invention, 2-atallyloyloxychetyl isocyanate (trade name: Power Lens A OI, Showa) Electric Works Co., Ltd.), 2-methacryloxy isocyanate (trade name: Power Lens MOI, Showa Denko Co., Ltd.) and the like.

[0239] また、本発明のポリマーの合成方法に用いられる溶媒としては、 SP値 (沖津法によ り算出）が 20〜23MPa1/2であるものが好ましぐ具体的には、エチレングリコールジ アセテート、ジエチレングリコールジアセテート、プロピレングリコールジアセテート、ァ セト酢酸メチル、ァセト酢酸ェチル、 1 , 2, 3—トリァセトキシ—プロパン、シクロへキサ ノン、 2—（1ーシクロへキセニノレ）シクロへキサノン、プロピオ二トリル、 N—メチルピロ リドン、ジメチルァセトアミド、ァセチルアセトン、ァセトフエノン、トリァセチン、 1 , 4ージ ォキサン、ジメチルカーボネート等が挙げられる。 [0239] The solvent used in the method for synthesizing the polymer of the present invention is preferably one having an SP value (calculated by the Okitsu method) of 20 to 23 MPa 1/2. Specifically, ethylene glycol Diacetate, Diethylene glycol diacetate, Propylene glycol diacetate, Methyl acetate acetate, Ethyl acetate acetate, 1,2,3-Triacetoxy-propane, Cyclohexanone, 2- (1-cyclohexenole) cyclohexanone, Propioni Tolyl, N-Methylpyrrolidone, Dimethylacetamide, Acetylacetone, Acetophenone, Triacetin, 1,4-di And oxane, dimethyl carbonate, and the like.

中でも、高分子量体を合成する観点から、エステル系溶媒であることがより好ましく 、特に、エチレングリコールジアセテート、ジエチレングリコールジアセテート等のジァ セテート系溶媒や、ジメチルカーボネートが更に好ましい。  Among these, from the viewpoint of synthesizing a high molecular weight substance, an ester solvent is more preferable, and a diacetate solvent such as ethylene glycol diacetate and diethylene glycol diacetate, and dimethyl carbonate are more preferable.

ここで、本発明における溶媒の SP値は、沖津法（沖津俊直著「日本接着学会誌」 2 9 (3) (1993) )によって算出したものである。具体的には、 SP値は以下の式で計算さ れるものである。なお、 A Fは文献記載の値である。  Here, the SP value of the solvent in the present invention is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula. A F is a value described in the literature.

[0240] 以上のようにして合成された本発明の二トリル基含有重合性ポリマーは、共重合成 分全体に対し、重合性基含有ユニット、二トリル基含有ユニットの割合が以下の範囲 であることが好ましい。 [0240] In the nitrile group-containing polymerizable polymer of the present invention synthesized as described above, the ratio of the polymerizable group-containing unit and the nitrile group-containing unit is in the following range with respect to the entire copolysynthesis component. It is preferable.

即ち、重合性基含有ユニットが、共重合成分全体に対し 5〜50mol%で含まれるこ と力 S好ましく、更に好ましくは 5〜40mol%である。 5mol%以下では反応性（硬化性 、重合性）が落ち、 50mol%以上では合成の際にゲル化しやすく合成しにくい。 また、二トリル基含有ユニットは、めっき触媒等に対する吸着性の観点から、共重合 成分全体に対し 5〜95mol%の範囲で含まれることが好ましぐ 10〜95mol%の範 囲で含まれることが更に好ましい。  That is, it is preferable that the polymerizable group-containing unit is contained in an amount of 5 to 50 mol% with respect to the entire copolymerization component, and more preferably 5 to 40 mol%. If it is less than 5 mol%, the reactivity (curability and polymerizability) is lowered, and if it is more than 50 mol%, it tends to gel during synthesis and is difficult to synthesize. Also, the nitrile group-containing unit should be included in the range of 10 to 95 mol%, preferably in the range of 5 to 95 mol% with respect to the entire copolymerization component, from the viewpoint of adsorptivity to the plating catalyst and the like. Is more preferable.

[0241] なお、本発明の二トリル基含有重合性ポリマーは、二トリル基含有ユニット、重合性 基含有ユニット以外に、他のユニットを含んでいてもよい。この他のユニットを形成す るために用いられるモノマーとしては、本発明の効果を損なわないものであれば、い 力、なるモノマーも使用することができる。  [0241] The nitrile group-containing polymerizable polymer of the present invention may contain other units in addition to the nitrile group-containing unit and the polymerizable group-containing unit. As the monomer used to form the other unit, a monomer that can be used can be used as long as the effects of the present invention are not impaired.

[0242] ただし、前述のように重合性基をポリマーに反応させて導入する場合は、 100%導 入することが困難な際には少量の反応性部分が残ってしまうことから、これが第 3のュ ニッ卜となる可倉 生あある。  [0242] However, when the polymerizable group is introduced after reacting with the polymer as described above, a small amount of the reactive portion remains when it is difficult to introduce 100%. There is a student Kakura who will be the unit.

上記の、二トリル基含有ユニット、重合性基含有ユニット以外の他のユニットを形成 するために用いられるモノマーの具体例としては、ラジカル重合でポリマー主鎖を形 成する場合は、ェチル (メタ）アタリレート、ブチル (メタ）アタリレート、へキシル (メタ）ァ タリレート、 2—ェチルへキシル（メタ）アタリレート、シクロへキシル（メタ）アタリレート、 ベンジル (メタ）アタリレート、ステアリル (メタ）アタリレートなどの無置換 (メタ）アクリル 酸エステノレ類、 2, 2, 2 トリフノレ才ロェチノレ（メタ）アタリレート、 3, 3, 3 トリフノレ才ロ プロピル（メタ）アタリレート、 2—クロ口ェチル（メタ）アタリレートなどのハロゲン置換（メ タ）アクリル酸エステル類、 2— (メタ）アクリルロイロキシェチルトリメチルアンモニゥム クロライドなどのアンモニゥム基置換 (メタ）アクリル酸エステル類、ブチル (メタ）アタリ タ）アクリルアミドなどの（メタ）アクリルアミド類、スチレン、ビュル安息香酸、 p—ビュル ベンジルアンモニゥムクロライドなどのスチレン類、 N ビュルカルバゾール、酢酸ビ ニル、 N ビュルァセトアミド、 N ビュル力プロラタタムなどのビュル化合物類や、そ の他にジメチルアミノエチル (メタ）アタリレート、ジェチルアミノエチル (メタ）アタリレー ト、 2—ェチルチオ—ェチル (メタ）アタリレート、 （メタ）アクリル酸、 2—ヒドロキシェチ ル (メタ）アタリレートなどが挙げられる。 Specific examples of monomers used to form units other than the nitrile group-containing unit and the polymerizable group-containing unit described above include ethyl (meth) when the polymer main chain is formed by radical polymerization. Atarylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, Unsubstituted (meth) acrylic acid esteres such as benzyl (meth) acrylate and stearyl (meth) acrylate, 2, 2, 2 Trifnore loyetinore (meth) acrylate, 3, 3, 3 Trifonole propyl (meta) ) Atalylates, halogen-substituted (meth) acrylic esters such as 2-cycloethyl (meth) acrylate, 2- (meth) acryloyllochichetyltrimethylammonium chloride substituted (meth) Acrylates, (meth) acrylamides such as butyl (meth) acrylamide), styrene, butylbenzoic acid, styrenes such as p-butylbenzyl ammonium chloride, N-butcarbazole, vinyl acetate, N-but Bulle compounds such as acetoamide and N-bull force prolatatum, and In addition, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, 2-ethyl thio-ethyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate Can be mentioned.

また、上記記載のモノマーを用いて得られたマクロモノマーも使用できる。  Moreover, the macromonomer obtained using the monomer of the said description can also be used.

[0243] カチオン重合でポリマー主鎖を形成する場合は、ェチルビュルエーテル、ブチルビ ニノレエーテノレ、イソブチノレビニノレエーテノレ、シクロへキシノレビニノレエーテノレ、ェチレ ングリコーノレビニノレエーテノレ、ジ（エチレングリコーノレ）ビニノレエーテノレ、 1 , 4 ブタン ジォーノレビニノレエーテノレ、 2—クロロェチノレビニノレエーテノレ、 2—ェチノレへキシノレビ ニノレエーテノレ、酢酸ビニノレ、 2—ビニノレオキシテトラヒドロピラン、ビニノレべンゾエート 、ビュルブチレートなどのビュルエーテル類、スチレン、 p クロロスチレン、 p メトキ シスチレンなどのスチレン類、ァリルアルコール、 4ーヒドロキシー 1ーブテンなどの末 端エチレン類を使用することができる。 [0243] When the polymer main chain is formed by cationic polymerization, ethyl butyl ether, butyl vinyl enoate, isobutino levino ree tenole, cyclohexeno levino ree tenole, ethylen glycino levino ree tenole, di ( (Ethylene glycolenole), vinylenoreethenore, 1,4 butanediolenolevininoleethenore, 2-chloroethinorevininoreethenore, 2-ethenorehexinolevininoreethenore, vinylinole acetate, 2-vininoreoxytetrahydropyran, Use can be made of vinyl ethers such as vinylolene benzoate and butyl butyrate, styrenes such as styrene, p-chlorostyrene, and p-methoxystyrene, terminal alcohols such as aryl alcohol, and 4-hydroxy-1-butene.

[0244] 本発明の二トリル基含有重合性ポリマーの重量平均分子量は、 1000以上 70万以 下が好ましぐ 2000以上 20万以下であることが更に好ましい。特に、重合感度の観 点から、本発明の二トリル基含有重合性ポリマーの重量平均分子量は、 20000以上 であることが好ましい。  [0244] The weight average molecular weight of the nitrile group-containing polymerizable polymer of the present invention is preferably 1000 or more and 700,000 or less, more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the nitrile group-containing polymerizable polymer of the present invention is preferably 20000 or more.

また、本発明の二トリル基含有重合性ポリマーの重合度としては、 10量体以上のも のを使用することが好ましぐ 20量体以上のものであることが更に好ましい。また、 70 00量体以下が好ましぐ 3000量体以下がより好ましぐ 2000量体以下が更に好まし く、 1000量体以下が特に好ましい。 The polymerization degree of the nitrile group-containing polymerizable polymer of the present invention is more preferably a 20-mer or more, preferably a 10-mer or more. In addition, 700-mer or less is preferable 3000-mer or less is more preferable 2000-mer or less is more preferable In particular, 1000-mer or less is particularly preferable.

[0245] 本発明の二トリル基含有重合性ポリマーの具体例を以下に示すが、これらに限定さ れるものではない。 [0245] Specific examples of the nitrile group-containing polymerizable polymer of the present invention are shown below, but are not limited thereto.

なお、これ 3000〜 100000の範囲で ある。  This is in the range of 3000-100000.

[0246] [化 28] マ [0246] [Chemical 28] Ma

Figure imgf000076_0001
Figure imgf000076_0001

[0247] [化 29] ~2) 態様で得られたポリマ- [0247] [Chemical 29] ~ 2) Polymer obtained in the embodiment

Figure imgf000077_0001
Figure imgf000077_0001

CN: t-2-10 1-2-Π CN: t-2-10 1-2-Π

- 1 ) 態様で得られたポリマ一-1) Polymer obtained in the embodiment

Figure imgf000078_0001
Figure imgf000078_0001

2-1 - 2

Figure imgf000078_0002
2-1-2
Figure imgf000078_0002

— 一 — One

Figure imgf000079_0001
Figure imgf000079_0001

] ]

— 2)態様で得られたポリマー — 2) Polymer obtained in the embodiment

:;ノ へ 、 CN :; No, CN

MeMe

- 、 ' 、、 ノ 20 、 SO-, ',, No 20, SO

CN び 、0 O f σ r j CN and 0 O f σ r j

- O CN

Figure imgf000080_0001
-O CN
Figure imgf000080_0001

2-2-17  2-2-17

2-2-21

Figure imgf000080_0002
2-2-21
Figure imgf000080_0002

Figure imgf000080_0003
3]
Figure imgf000080_0003
3]

-2) 態様で得られたポリマ- N-2) Polymer obtained in the embodiment-N

Figure imgf000081_0001
Figure imgf000081_0001

4] Four]

2 - 2 態様で得 マ一2-2 gained in one aspect

Figure imgf000082_0001
Figure imgf000082_0001

Figure imgf000082_0002
Figure imgf000082_0002

[0253] ここで、例えば、前記具体例の化合物 2— 2— 11は、アクリル酸と 2—シァノエチル アタリレートを、例えば、 N—メチルピロリドンに溶解させ、重合開始剤として、例えば 、ァゾイソブチロニトリル (AIBN)を用いてラジカル重合を行い、その後、グリシジルメ タクリレートをべンジノレトリェチルアンモニゥムクロライドのような触媒を用い、ターシャ リーブチルノヽイドロキノンのような重合禁止剤を添加した状態で付加反応することで 合成すること力でさる。  [0253] Here, for example, in the compound 2-2-11 of the above specific example, acrylic acid and 2-cyanoethyl acrylate are dissolved in, for example, N-methylpyrrolidone, and the polymerization initiator is, for example, azoisobut Perform radical polymerization using tyronitrile (AIBN), and then add glycidyl methacrylate with a catalyst such as benzyltrityl ammonium chloride and a polymerization inhibitor such as tertiary butyl nodroquinone. It is the power of synthesis by reacting.

また、例えば、前記具体例の化合物 2— 2— 19は、以下のモノマーと、 p—シァノベ ンジルアタリレートを、 N、 N—ジメチルアクリルアミドのような溶媒に溶解させ、ァゾィ ソ酪酸ジメチルのような重合開始剤を用いてラジカル重合を行い、その後、トリェチル ァミンのような塩基を用いて脱塩酸を行うことで合成することができる。  In addition, for example, in the compound 2-2-19 in the above specific example, the following monomers and p-cyanobenzatylate are dissolved in a solvent such as N, N-dimethylacrylamide, and dimethyl azobutyrate is used. It can be synthesized by performing radical polymerization using a suitable polymerization initiator and then dehydrochlorinating using a base such as triethylamine.

[0254] [化 35]  [0254] [Chemical 35]

Figure imgf000082_0003
[0255] 本発明の二トリル基含有重合性ポリマーは、例えば、 pH12のアルカリ性溶液に添 加し、 1時間攪拌したときの重合性基部位の分解が 50%以下である場合は、該ポリ マーに対して高アルカリ性溶液による洗浄を行うことができる。
Figure imgf000082_0003
[0255] The nitrile group-containing polymerizable polymer of the present invention is, for example, added to an alkaline solution having a pH of 12 and stirred for 1 hour when the decomposition of the polymerizable group site is 50% or less. Can be washed with a highly alkaline solution.

[0256] 本発明の新規ポリマーの使用態様 [0256] Usage of the novel polymer of the present invention

本発明の二トリル基含有重合性ポリマーは、二トリル基を有するユニットと、重合性 基を有するユニットとの共重合体であるため、ユニットの比を変化させることで、めっき 触媒等の金属に対する吸着性と、重合性 (反応性)と、を制御すること力 Sできる。 このような本発明の二トリル基含有重合性ポリマーは、光硬化性樹脂組成物の他、 成型材料、コーティング材料、表面改質材料、基板用材料として電子分野、機械分 野、食品分野、建築分野、自動車分野において用いることができる。  Since the nitrile group-containing polymerizable polymer of the present invention is a copolymer of a unit having a nitrile group and a unit having a polymerizable group, by changing the ratio of the units, it can be applied to a metal such as a plating catalyst. The ability to control adsorption and polymerization (reactivity) can be controlled. Such a nitrile group-containing polymerizable polymer of the present invention is not only a photocurable resin composition but also a molding material, a coating material, a surface modifying material, and a substrate material in the electronic field, the mechanical field, the food field, and the construction field. It can be used in the field and the automobile field.

[0257] 種々の用途の中でも、疎水性であるにも関わらず、めっき触媒に対する吸着性と重 合性に優れる点から、本発明の二トリル基含有重合性ポリマーは、めっき膜を形成す るための表面処理材料として用いられることが好ましい。 [0257] Among various uses, the nitrile group-containing polymerizable polymer of the present invention forms a plating film because it is hydrophobic and has excellent adsorptivity and polymerizability to the plating catalyst. It is preferable to be used as a surface treatment material.

例えば、本発明の二トリル基含有重合性ポリマーを、表面グラフト重合法などを用い 、所望の基材上に直接化学結合させることで、基材との密着性が高ぐめっき触媒に 対する吸着性に優れ、更に、吸水性の少ないポリマー層を形成することができる。こ のポリマー層上にめっき触媒を付与し、その後、めっき処理を施すことで形成された めっき膜は、ポリマー層との密着性が優れるといった効果と共に、ポリマー層が水分 やイオン等を保持し難いため、温'湿度依存性や、形状の変化が見られないといった 効果も有する。  For example, the nitrile group-containing polymerizable polymer of the present invention is directly adsorbed onto a desired substrate using a surface graft polymerization method or the like, thereby adsorbing to a plating catalyst having high adhesion to the substrate. In addition, a polymer layer with low water absorption can be formed. The plating film formed by applying a plating catalyst on this polymer layer and then performing a plating treatment has the effect of excellent adhesion to the polymer layer, and the polymer layer is difficult to retain moisture, ions, etc. Therefore, there are effects such as temperature and humidity dependence and no change in shape.

特に、このめつき膜が形成された基材を、電気配線等の製造に用いる際には、配線 間の絶縁信頼性に優れるといった効果も奏する。  In particular, when the base material on which the adhesive film is formed is used for manufacturing electrical wiring or the like, there is an effect that the insulation reliability between the wirings is excellent.

なお、めっき膜が形成された基材には、エポキシ樹脂、ポリイミド樹脂、又は PET樹 脂を含有する樹脂基材を用いることが好ましレ、。  For the substrate on which the plating film is formed, it is preferable to use a resin substrate containing an epoxy resin, a polyimide resin, or a PET resin.

[0258] なお、本発明の二トリル基含有重合性ポリマーは、他の成分 (例えば、溶剤）と混合 して組成物として使用すること力 Sできる。その場合、本発明の二トリル基含有重合性ポ リマーの含有量は、該組成物の全重量に対して 2質量％〜50質量％の範囲にあるこ と力 S好ましく、 5質量％〜30質量％の範囲にあることがより好ましい。 [0258] The nitrile group-containing polymerizable polymer of the present invention can be used as a composition by mixing with other components (for example, a solvent). In that case, the content of the nitrile group-containing polymerizable polymer of the present invention should be in the range of 2% by mass to 50% by mass with respect to the total weight of the composition. And force S, preferably in the range of 5% by mass to 30% by mass.

[0259] 本発明の二トリル基含有重合性ポリマーを含有する組成物に使用する溶剤は、該 ポリマーが溶解可能ならば特に制限はない。また、溶剤には、更に、界面活性剤を添 加してもよい。 [0259] The solvent used in the composition containing the nitrile group-containing polymerizable polymer of the present invention is not particularly limited as long as the polymer can be dissolved. Further, a surfactant may be further added to the solvent.

使用できる溶剤の具体例は、前記重合性基及び相互作用性基を有する化合物（例 えば、シァノ基含有重合性ポリマー）の組成物において使用可能な溶剤の具体例と 同様であり、その好適な具体例もまた同様である。また、本発明の二トリル基含有重 合性ポリマーを含有する組成物を塗布用途に適用する場合の各種条件 (例えば、組 成物の温度、各成分の濃度、添加物などの条件)も、前記シァノ基含有重合性ポリマ 一を含有する組成物を塗布する場合の各種条件と同様である。  Specific examples of the solvent that can be used are the same as the specific examples of the solvent that can be used in the composition of the compound having a polymerizable group and an interactive group (for example, a cyano group-containing polymerizable polymer). The specific example is also the same. In addition, various conditions (for example, the temperature of the composition, the concentration of each component, the conditions of additives, etc.) when the composition containing the nitrile group-containing polymerizable polymer of the present invention is applied to coating applications are also included. The same conditions as those in the case of applying the composition containing the cyano group-containing polymerizable polymer.

[0260] 本発明の二トリル基含有重合性ポリマーを含有する組成物を用いて積層体を形成 する際に用いられる基材としては、寸度的に安定な板状物が好ましぐ必要な可撓性 、強度、耐久性等を満たせばいずれのものも使用でき、使用目的に応じて適宜選択 される。 [0260] As a base material used for forming a laminate using the composition containing the nitrile group-containing polymerizable polymer of the present invention, a dimensionally stable plate-like material is preferably used. Any material can be used as long as it satisfies flexibility, strength, durability, etc., and is appropriately selected according to the purpose of use.

具体的には、例えば、ポリイミド樹脂、ビスマレインイミド樹脂、ポリフエ二レンォキサ イド樹脂、エポキシ樹脂、液晶ポリマー、ポリテトラフルォロエチレン樹脂などを成型し たものや、シリコーン基板、紙、プラスチックがラミネートされた紙、金属板（例えば、ァ ノレミニゥム、亜鉛、銅等）、上記の如き金属がラミネート若しくは蒸着された紙若しくは プラスチックフイノレム等を挙げることカできる。  Specifically, for example, polyimide resin, bismaleimide resin, polyphenylene oxide resin, epoxy resin, liquid crystal polymer, polytetrafluoroethylene resin, etc., silicone substrates, paper, and plastic are laminated. Paper, metal plate (for example, ano-remium, zinc, copper, etc.), paper or plastic vinyl on which a metal as described above is laminated or vapor-deposited.

なお、前述のように、基材上に二トリル基含有重合性ポリマーを用いてめっき膜を形 成し、このめつき膜をプリント配線板の作製に適用する場合には、基材として絶縁性 樹脂からなるものを用いることが好ましレ、。  As described above, when a plated film is formed on a base material using a nitrile group-containing polymerizable polymer and this adhesive film is applied to the production of a printed wiring board, the base material is insulative. It is preferable to use resin.

実施例  Example

[0261] 以下、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるも のではない。なお、特に断りのない限り、「％」「部」は質量基準である。  [0261] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Unless otherwise specified, “%” and “part” are based on mass.

[0262] 実施例 1 1  [0262] Example 1 1

基板の作製  Fabrication of substrate

ガラスエポキシ基板上に、電気的絶縁層として味の素ファインテクノ社製エポキシ 系絶縁膜 GX— 13 (商品名、膜厚: 45 111)を、加熱、加圧して、真空ラミネーターに より 0. 2MPaの圧力で 100°C〜110°Cの条件により接着して、基材を得た。 Epoxy made by Ajinomoto Fine-Techno Co., Ltd. as an electrical insulation layer on a glass epoxy board The base insulating film GX-13 (trade name, film thickness: 45 111) is heated and pressurized, and is bonded by a vacuum laminator at a pressure of 0.2 MPa under the conditions of 100 ° C to 110 ° C. Got.

ついで、基材の上に、下記組成の重合開始剤を含有する絶縁性組成物を厚さ 3ミ クロンになるようにスピンコート法で塗布し、 30°Cにて 1時間放置して溶剤を除去した 後、 140°Cで 30分乾燥して重合開始層（絶縁性の重合開始層）を形成した。  Next, an insulating composition containing a polymerization initiator having the following composition was applied onto the substrate by spin coating so as to have a thickness of 3 microns, and left at 30 ° C for 1 hour to remove the solvent. After removal, it was dried at 140 ° C. for 30 minutes to form a polymerization initiation layer (insulating polymerization initiation layer).

[0263] 重合開始剤を含有する絶縁性組成物 [0263] Insulating composition containing polymerization initiator

ビスフエノール A型エポキシ樹脂（エポキシ当量： 185、油化シェルエポキシ (株）製 、商品名：ェピコート 828) 20質量部、クレゾールノポラック型エポキシ樹脂（エポキシ 当量 215、大日本インキ化学工業 (株)製、商品名：ェピクロン N— 673) 45質量部、 フエノールノポラック樹脂（フエノール性水酸基当量 105、大日本インキ化学工業 (株 )製、商品名：フエノライト） 30質量部を、ェチルジグリコールアセテート 20部、及びソ ルベントナフサ 20部に、攪拌しながら加熱溶解させ室温まで冷却した後、そこへ前 記ェピコート 828とビスフエノール Sとからなるフエノキシ樹脂のシクロへキサノンヮニ ス（油化シェルエポキシ (株)製、商品名： YL6747H30、不揮発分 30質量％、重量 平均分子量 47000) 30質量部、 2—フエ二ルー 4, 5—ビス（ヒドロキシメチル）イミダゾ 一ノレ 0. 8質量部、微粉砕シリカ 2質量部、シリコン系消泡剤 0. 5質量部を添加し、更 にこの混合物中に、下記の方法で合成した重合開始ポリマー Pを 10部添加し、重合 開始剤を含有する絶縁性組成物を得た。  Bisphenol A type epoxy resin (epoxy equivalent: 185, manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 828) 20 parts by mass, cresol nopolac type epoxy resin (epoxy equivalent: 215, Dainippon Ink & Chemicals, Inc.) Product name: Epiclone N—673) 45 parts by mass, phenol nopolac resin (phenolic hydroxyl group equivalent 105, manufactured by Dainippon Ink & Chemicals, Inc., trade name: Phenolite) 30 parts by mass, ethyl diglycol acetate In 20 parts and 20 parts of sorbent naphtha, the mixture is heated and dissolved with stirring and cooled to room temperature. Then, cyclohexanone succinic acid, a phenoxy resin composed of Epicoat 828 and bisphenol S (Oka Shell Epoxy Co., Ltd.) Product name: YL6747H30, non-volatile content 30% by mass, weight average molecular weight 47000) 30 parts by mass, 2-phenol 4, 5-bis (hydroxyme I) Imidazo Ichinole 0.8 parts by mass, finely pulverized silica 2 parts by mass, silicon-based antifoaming agent 0.5 parts by mass were added, and polymerization initiator polymer P synthesized by the following method was added to this mixture. 10 parts was added to obtain an insulating composition containing a polymerization initiator.

[0264] 重合開始ポリマー Pの合成 [0264] Synthesis of Polymer P

300mlの三口フラスコに、プロピレングリコールモノメチルエーテル（MFG) 30gを 加え 75度に加熱した。そこに、 [2— (Acryloyloxy) ethyl] (4 -benzoylbenzyl) di methyl ammonium bromide8. igと、 2— HydroxyethylmetJ aacrylate9. 9 gと、 isopropylmethaacrylatel 3. 5gと、ジメチノレー 2, 2， 一ァゾビス（2—メチルプ 口ピオネート） 0· 43gと、 MFG30gと、の溶液を 2· 5時間かけて滴下した。その後、 反応温度を 80度に上げ、更に 2時間反応させ、重合開始基を有するポリマー Pを得 た。  To a 300 ml three-necked flask, 30 g of propylene glycol monomethyl ether (MFG) was added and heated to 75 degrees. Then, [2— (Acryloyloxy) ethyl] (4-benzoylbenzyl) dimethyl ammonium bromide8.ig, 2-hydroxyxymetmetacrylate 9.9 g, isopropylmethaacrylatel 3.5 g, dimethylolene 2, 2, monoazobis Mouth Pionate) A solution of 0 · 43 g and MFG 30 g was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain a polymer P having a polymerization initiating group.

[0265] 上記のような重合開始層が形成された後、 180°Cで 30分間硬化処理を実施した。  [0265] After the polymerization initiation layer as described above was formed, curing treatment was performed at 180 ° C for 30 minutes.

これにより、基板 A1を得た。この基板 A1の表面凹凸（Rz)は 0. 2〃mであった。 [0266] ポリマー層の形成 Thereby, a substrate A1 was obtained. The surface roughness (Rz) of this substrate A1 was 0.2 mm. [0266] Formation of polymer layer

重合性基及び相互作用性基を有するポリマー Aの合成  Synthesis of polymer A with polymerizable and interacting groups

まず、下記のようにして、重合性基及び相互作用性基を有するポリマー Aを合成し た。  First, Polymer A having a polymerizable group and an interactive group was synthesized as follows.

1000mlの三口フラスコに、 N, N—ジメチルァセトアミド 35gを入れ、窒素気流下、 75°Cまで加熱した。そこへ、 2—ヒドロキシェチルアタリレート（市販品、東京化成製） 6. 60g、 2—シァノエチルアタリレート 28· 4g、ァゾビスイソ酪酸メチル（商品名： V— 601、和光純薬製） 0· 65gの N, N—ジメチノレアセトアミド 35g溶 ί夜を、 2. 5日寺間力、け て滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温まで 、反応溶液を冷却した。  In a 1000 ml three-necked flask, 35 g of N, N-dimethylacetamide was placed and heated to 75 ° C. under a nitrogen stream. There, 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.) 6. 60 g, 2-cyanoethyl acrylate 28.4 g, methyl azobisisobutyrate (trade name: V-601, manufactured by Wako Pure Chemical Industries) 0 · 65 g of N, N-dimethylenoacetamide 35 g was added dropwise for 2.5 days. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 29g、ジブチルチンジラ ゥレート 0. 29g、力レンズ AOI (商品名、昭和電工（株）製） 18. 56g、 N, N—ジメチ ルァセトアミド 19gを加え、 55°C、 4時間反応を行った。その後、反応液にメタノール を 3. 6g加え、更に 1. 5時間反応を行った。反応終了後、酢酸ェチル：へキサン = 1 : 1で再沈を行い、固形物を取り出し、重合性基及び相互作用性基を有するポリマー A (重量平均分子量 1. 5万）を 32g得た。  Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, power lens AOI (trade name, manufactured by Showa Denko KK) 18. 56 g, N, N-dimethylacetamide 19 g are added to the above reaction solution, The reaction was carried out at 55 ° C for 4 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane = 1: 1, and the solid matter was taken out to obtain 32 g of polymer A having a polymerizable group and an interactive group (weight average molecular weight 150,000).

[0267] 塗布溶液の調製  [0267] Preparation of coating solution

重合性基及び相互作用性基を有するポリマー A: 10. 5質量部、アセトン 73. 3質 量部、メタノール 33. 9質量部、及び N, Nジメチルァセトアミド 4. 8質量部を混合攪 拌し、塗布溶液を調製した。  Polymer A having a polymerizable group and an interactive group A: 10.5 parts by mass, 73.3 parts by mass of acetone, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide Stir to prepare a coating solution.

[0268] グラフトポリマーの生成  [0268] Formation of graft polymer

調製された塗布溶液を、前記基板 A1の重合開始層上に、厚さ 1 μ mになるように、 スピンコート法により塗布し、 80°Cにて 30分乾燥した後、三永電機製の UV露光機（ 商品名： UVF— 502S、ランプ： UXM— 501MD)を用い、 1. 5mW/cm2の照射パ ヮー（ゥシォ電機製の紫外線積算光量計（商品名： UIT150)及び受光センサー（商 品名： UVD— S254)により測定）にて、 660秒間照射させて、基板 A1の重合開始層 の全面にグラフトポリマーを生成させた。ここで、積算露光量は 990mJであった。 The prepared coating solution was applied onto the polymerization initiation layer of the substrate A1 by a spin coating method so as to have a thickness of 1 μm and dried at 80 ° C. for 30 minutes. UV exposure machine (trade name: UVF- 502S, lamp: UXM- 501MD) using, 1. 5mW / cm 2 of irradiation path Wa (Ushio Denki manufactured accumulated UV actinometer (trade name: UIT150) and a light receiving sensor (quotient The product was irradiated for 660 seconds under the product name: UVD—S254) to produce a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1. Here, the integrated exposure was 990 mJ.

[0269] その後、攪拌した状態のアセトン中にグラフトポリマーが生成された基板を 5分間浸 漬し、続いて、蒸留水にて洗浄した。 [0269] Then, the substrate on which the graft polymer was formed was immersed in acetone in a stirred state for 5 minutes. It was pickled and subsequently washed with distilled water.

これにより、ポリマー層を有する基板 A2を得た。  Thereby, a substrate A2 having a polymer layer was obtained.

[0270] ポリマー層の物性測定 [0270] Measurement of physical properties of polymer layer

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

•25°C— 50%相対湿度環境下における飽和吸水率： 1. 2質量％  • Saturated water absorption rate at 25 ° C—50% relative humidity: 1.2% by mass

•25°C— 95%相対湿度環境下における飽和吸水率： 3. 4質量％  • Saturated water absorption at 25 ° C—95% relative humidity: 3.4% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 7. 5質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.5% by mass

•25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置後の表 面接触角： 70. 3度  • 25 ° C—Surface contact angle after dripping 5 ^ L of distilled water in a 50% relative humidity environment and allowing to stand for 15 seconds: 70.3 degrees

[0271] めっき触媒の付与 [0271] Application of plating catalyst

ポリマー層を有する基板 A2を、硝酸パラジウムの 1 %アセトン溶液に、 30分間浸漬 した後、アセトンに浸漬して洗浄した。  Substrate A2 having a polymer layer was immersed in a 1% acetone solution of palladium nitrate for 30 minutes, and then immersed in acetone for cleaning.

続いて、 1 %ジメチルポラン一水/メタノール (水/メタノール = 1/3)混合溶液を 触媒活性化液 (還元液）として用い、この溶液中に、ポリマー層を有する基板 A2を 15 分浸漬させた後、アセトンに浸漬し洗浄を行った。  Subsequently, a 1% dimethylporane monohydrate / methanol (water / methanol = 1/3) mixed solution was used as a catalyst activation liquid (reducing liquid), and a substrate A2 having a polymer layer was immersed in this solution for 15 minutes. Then, it was immersed in acetone for cleaning.

[0272] 無電解めつき [0272] Electroless plating

上記のようにして、めっき触媒が付与されたポリマー層を有する基板 A2に対し、下 記組成の無電解めつき浴を用い、 60°Cで 5分間、無電解めつきを行った。得られた 無電解銅めつき膜の厚みは 0· 3 mであった。  As described above, electroless plating was carried out at 60 ° C. for 5 minutes using the electroless plating bath having the following composition on the substrate A2 having a polymer layer provided with a plating catalyst. The thickness of the obtained electroless copper plating film was 0.3 m.

[0273] 無電解めつき浴の組成  [0273] Composition of electroless bath

•蒸留水 859g  • 859g of distilled water

•メタノーノレ 850g • Methanore 8 50g

'硫酸銅 18. lg 'Copper sulfate 18. lg

'エチレンジァミン四酢酸.2ナトリウム塩 54. Og  'Ethylenediamine tetraacetic acid.2 sodium salt 54. Og

•ポリオキシエチレングリコール（分子量 1000) 0. 18g  • Polyoxyethylene glycol (molecular weight 1000) 0.18g

•2, 2，ビビリジノレ 1 · 8mg  • 2, 2, bibilidinole 1 · 8mg

•10%エチレンジァミン水溶液 7. lg 以上の組成のめっき浴の pHを、水酸化ナトリウム及び硫酸で 12. 5 (60°C)に調整 した。 • 10% ethylenediamine aqueous solution 7. lg The pH of the plating bath having the above composition was adjusted to 12.5 (60 ° C) with sodium hydroxide and sulfuric acid.

[0274] 電気めつき  [0274] Electric plating

続いて、無電解銅めつき膜を給電層として、下記組成の電気銅めつき浴を用い、 3 Subsequently, using an electroless copper plating film as a feeding layer, an electrolytic copper plating bath having the following composition was used:

A/dm2の条件で、電気めつきを 20分間行った。得られた電気銅めつき膜の厚みはUnder the conditions of A / dm 2, it was subjected to electrophoresis plated for 20 minutes. The thickness of the obtained electrolytic copper plating film is

18 / mであつに。 18 / m.

[0275] 電気めつき浴の組成 [0275] Composition of electric bath

'硫酸銅 38g  'Copper sulfate 38g

'硫酸 95g  'Sulfuric acid 95g

•塩酸 lmL  Hydrochloric acid lmL

•カッパーグリーム PCM (商品名、メルテックス（株）製） 3mL  • Copper Grime PCM (trade name, manufactured by Meltex Co., Ltd.) 3mL

•水 500g  • Water 500g

[0276] 密着性評価 [0276] Adhesion evaluation

得られためっき膜に対して、引張試験機（(株)エー'アンド '·デー製、商品名： RTM 100)を用いて、 5mm幅について、引張強度 10mm/minにて、 90° ピール強度 の測定を行ったところ、 0. 7kN/mmであった。  Using the tensile tester (trade name: RTM 100, manufactured by A & D Co., Ltd.) for the obtained plated film, 90 ° peel strength at a tensile strength of 10 mm / min for a width of 5 mm The measurement was 0.7 kN / mm.

[0277] 金属パターンの形成、及び絶縁信頼性試験 [0277] Formation of metal pattern and insulation reliability test

得られためっき膜表面に、金属パターン (配線パターン）として残すべき領域にエツ チングレジストを形成し、レジストのない領域のめっき膜を、 FeCl /HC1からなるエツ  On the surface of the obtained plating film, an etching resist is formed in a region to be left as a metal pattern (wiring pattern), and a plating film in a region having no resist is formed by etching with FeCl / HC1.

3  Three

チング液により除去した。その後、エッチングレジストを 3%NaOH液からなるアルカリ 剥離液にて除去し、ライン'アンド 'スペース = 100 μ m/100 μ mの線間絶縁信頼 性を測定するための櫛形配線 (金属パターン材料)を形成した。  It was removed with a ching solution. Then, the etching resist is removed with an alkaline stripping solution consisting of 3% NaOH solution, and comb-shaped wiring (metal pattern material) is used to measure the insulation reliability between lines 'and' space = 100 μm / 100 μm. Formed.

この櫛形配線を、 HAST試験機（商品名： AMI— 150S— 25、 ESPEC製）にて、 1 25°C— 85%相対湿度（未飽和）、印加電圧 10V、 2気圧下で 200時間放置させた所 、配線間の絶縁不良は見られな力 た。  This comb-shaped wiring is allowed to stand for 200 hours under a HAST tester (trade name: AMI—150S-25, manufactured by ESPEC) at 125 ° C—85% relative humidity (unsaturated), applied voltage of 10 V, and 2 atm. As a result, no insulation failure was observed between the wires.

[0278] 実施例 1 2 [0278] Example 1 2

実施例 1 1で作製した、重合開始層が形成された基板 A1を用い、以下のようにし て表面金属膜材料を作製した。 Example 11 Using the substrate A1 formed with the polymerization initiation layer prepared in Example 1, the following was performed. Thus, a surface metal film material was prepared.

[0279] ポリマー層の形成 [0279] Formation of polymer layer

重合性基及び相互作用性基を有するポリマー Bの合成  Synthesis of polymer B with polymerizable and interacting groups

まず、下記のようにして、重合性基及び相互作用性基を有するポリマー Bを合成し た。  First, Polymer B having a polymerizable group and an interactive group was synthesized as follows.

1000mlの三口フラスコに、 N, N—ジメチルァセトアミド 42gを入れ、窒素気流下、 75°Cまで加熱した。そこへ、 2—ヒドロキシェチルアタリレート（市販品、東京化成製） 5. 6g、アタリノレ酸 2—（2—ェ卜キシェ卜キシ）ェチノレ 36. lg、 V— 601 (前述） 0. 55g の N—ジメチルァセトアミド 42g溶液を、 2. 5時間かけて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温まで、反応溶液を冷却した。 上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 24g、ジブチルチンジラ ゥレート 0. 30g、力レンズ AOI (商品名、昭和電工（株）製） 15. 5g、 N, N—ジメチル ァセトアミド 16gを加え、 55°C、 4時間反応を行った。その後、反応液にメタノールを 3 . lg加え、更に 1. 5時間反応を行った。反応終了後、蒸留水で再沈を行い、固形物 を取り出し、重合性基及び相互作用性基を有するポリマー B (重量平均分子量 1. 7 万）を 30g得た。  In a 1000 ml three-necked flask, 42 g of N, N-dimethylacetamide was placed and heated to 75 ° C. under a nitrogen stream. There, 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.) 5.6 g, Atalinoleic acid 2- (2-Echixoxy) ethynole 36. lg, V- 601 (above) 0.55 g A 42 g solution of N-dimethylacetamide was added dropwise over 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature. Ditertiary butyl hydroquinone 0.24 g, dibutyltin dilaurate 0.30 g, power lens AOI (trade name, manufactured by Showa Denko KK) 15.5 g, N, N-dimethylacetamide 16 g are added to the above reaction solution, The reaction was carried out at 55 ° C for 4 hours. Thereafter, 3. lg of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with distilled water, and the solid matter was taken out to obtain 30 g of polymer B having a polymerizable group and an interactive group (weight average molecular weight 17,000).

[0280] 塗布溶液の調整 [0280] Preparation of coating solution

重合性基及び相互作用性基を有するポリマー B : 7. 9質量部、イソプロパノール 73 . 3質量部、メタノール 33. 9質量部、及び N, Nジメチルァセトアミド 4. 8質量部を混 合攪拌し、塗布溶液を調製した。  Polymer B having polymerizable group and interactive group B: 7.9 parts by mass, 73.3 parts by mass of isopropanol, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide Then, a coating solution was prepared.

[0281] グラフトポリマーの生成 [0281] Formation of graft polymer

調製された塗布溶液を、スピンコートにて前記基板 A1の重合開始層上に、厚さ 1 μ mになるように、スピンコート法により塗布し、 80°Cにて 30分乾燥した後、三永電機製 の UV露光機（商品名： UVF— 502S、ランプ： UXM— 501MD)を用い、 1. 5mW /cm2の照射パワー（ゥシォ電機製の紫外線積算光量計（商品名： UIT150)及び受 光センサー（商品名： UVD— S254)により測定)）にて、 660秒間照射させて、基板 A1の重合開始層の全面にグラフトポリマーを生成させた。ここで、積算露光量は 990 mjであった。 [0282] その後、攪拌した状態のメタノール中にグラフトポリマーが生成された基板を 5分間 浸漬し、続いて、蒸留水にて洗浄した。 The prepared coating solution is applied by spin coating to a thickness of 1 μm on the polymerization initiation layer of the substrate A1 by spin coating, dried at 80 ° C. for 30 minutes, Using a UV exposure machine (product name: UVF-502S, lamp: UXM-501MD) manufactured by Electrical Electric Co., Ltd., with an irradiation power of 1.5 mW / cm 2 (ultraviolet integrated photometer (product name: UIT150) manufactured by Usio Electric Co., Ltd.) The photopolymer (trade name: measured by UVD—S254)) was irradiated for 660 seconds to form a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1. Here, the integrated exposure was 990 mj. [0282] Thereafter, the substrate on which the graft polymer was produced was immersed in methanol in a stirred state for 5 minutes, and then washed with distilled water.

これにより、ポリマー層を有する基板 A3を得た。  Thereby, a substrate A3 having a polymer layer was obtained.

[0283] ポリマー層の物性測定 [0283] Measurement of physical properties of polymer layer

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

• 25°C - 50%相対湿度環境下における飽和吸水率： 0. 8質量％  • Saturated water absorption at 25 ° C-50% relative humidity: 0.8% by mass

• 25°C— 95 %相対湿度環境下における飽和吸水率： 3. 0質量％  • Saturated water absorption at 25 ° C—95% relative humidity: 3.0% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 5. 5質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 5.5% by mass

•25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置後の表 面接触角： 83. 9度  • 25 ° C—Surface contact angle after dropping 15 mL of distilled water in a 50% relative humidity environment for 15 seconds: 83.9 degrees

[0284] 続いて、このポリマー層を有する基板 A3に対して、実施例 1 1と同様の方法で、 めっき触媒の付与、無電解めつき、及び電気めつきを行った。  [0284] Subsequently, application of a plating catalyst, electroless plating, and electroplating were performed on the substrate A3 having the polymer layer in the same manner as in Example 11.

[0285] 密着性評価 [0285] Adhesion evaluation

得られためっき膜に対して、引張試験機（(株)エー'アンド '·デー製、商品名： RTM 100)を用いて、 5mm幅について、引張強度 10mm/minにて、 90° ピール強度 の測定を行ったところ、 0. 67kN/mmであった。  Using the tensile tester (trade name: RTM 100, manufactured by A & D Co., Ltd.) for the obtained plated film, 90 ° peel strength at a tensile strength of 10 mm / min for a width of 5 mm The measurement was 0.67 kN / mm.

[0286] 金属パターンの形成、及び絶縁信頼性試験 [0286] Formation of metal pattern and insulation reliability test

得られためっき膜表面に、金属パターン (配線パターン）として残すべき領域にエツ チングレジストを形成し、レジストのない領域のめっき膜を、 FeCl /HC1からなるエツ  On the surface of the obtained plating film, an etching resist is formed in a region to be left as a metal pattern (wiring pattern), and a plating film in a region having no resist is formed by etching with FeCl / HC1.

3  Three

チング液により除去した。その後、エッチングレジストを 3%NaOH液からなるアルカリ 剥離液にて除去し、ライン'アンド 'スペース = 100 μ m/100 μ mの線間絶縁信頼 性を測定するための櫛形配線 (金属パターン材料)を形成した。  It was removed with a ching solution. Then, the etching resist is removed with an alkaline stripping solution consisting of 3% NaOH solution, and comb-shaped wiring (metal pattern material) is used to measure the insulation reliability between lines 'and' space = 100 μm / 100 μm. Formed.

この櫛形配線を、 ESPEC製 HAST試験機（商品名： AMI— 150S— 25)にて、 12 5°C— 85%相対湿度（未飽和）、印加電圧 10V、 2気圧下で 200時間放置させた所、 配線間の絶縁不良は見られな力、つた。  This comb-shaped wiring was allowed to stand for 200 hours at 125 ° C—85% relative humidity (unsaturated), an applied voltage of 10 V, and 2 atm using an ESPEC HAST tester (trade name: AMI—150S-25). However, the insulation failure between the wires was unseen.

[0287] 実施例 1 3 [0287] Example 1 3

基板の作製 ポリイミドフィルム（商品名：カプトン 500H、東レデュポン社製）からなる基材上に、 下記の重合開始層塗布液を、ロッドバー 18番を用いて塗布し、 110°Cで 10分乾燥- 架橋反応させた。得られた重合開始層の膜厚は 9. 3 111であった。このようにして得 られた基板を基板 B1とした。得られた基板 B1の表面凹凸（Rz)は 0. 3 mであったFabrication of substrate The following polymerization initiation layer coating solution is applied to a substrate made of a polyimide film (trade name: Kapton 500H, manufactured by Toray DuPont) using a rod bar No. 18 and dried at 110 ° C for 10 minutes to undergo crosslinking reaction It was. The film thickness of the obtained polymerization initiation layer was 9.3 111. The substrate thus obtained was designated as substrate B1. The surface roughness (Rz) of the obtained substrate B1 was 0.3 m.

〇 Yes

[0288] 重合開始層塗布液  [0288] Coating liquid for polymerization initiation layer

•前記重合開始ポリマー P 0. 4g  • Polymerization initiation polymer P 0.4 g

•TDI (トリレン 2, 4 ジイソシァネート） 0. 16g  • TDI (Tolylene 2, 4 Diisocyanate) 0.16g

-メチルェチルケトン（MEK) 1. 6g  -Methyl ethyl ketone (MEK) 1.6 g

[0289] ポリマー層の形成  [0289] Formation of polymer layer

塗布溶液の調製  Preparation of coating solution

前記重合性基及び相互作用性基を有するポリマー A: 10. 5質量部、メチルェチル ケトン（ΜΕΚ) 73· 3質量部、メタノーノレ 33. 9質量部、及び Ν, Νジメチルァセトアミド 4. 8質量部を混合攪拌し、塗布溶液を調製した。  Polymer A having Polymerizable Group and Interactive Group A: 10.5 parts by mass, 7-3 parts by mass of methyl ethyl ketone (ΜΕΚ), 33.9 parts by mass of methanol, and Ν, Ν dimethylacetamide 4.8 parts by mass Parts were mixed and stirred to prepare a coating solution.

[0290] グラフトポリマーの生成 [0290] Formation of graft polymer

調製された塗布溶液を、前記基板 B1の重合開始層上に、実施例 1 1と同様の方 法でスピンコートした後、乾燥し、 UV露光機（商品名： UVF— 502S、ランプ： UXM 501MD、三永電機製）を用い、 1. 5mW/cm2の照射パワー（ゥシォ電機製の紫 外線積算光量計（商品名： UIT150)及び受光センサー（商品名： UVD— S254)に より測定)）にて、 800秒間照射させて、基板 B1の重合開始層の全面にグラフトポリマ 一を生成させた。ここで、積算露光量は 1200mJであった。 The prepared coating solution was spin-coated on the polymerization initiation layer of the substrate B1 in the same manner as in Example 11 and then dried, followed by drying with a UV exposure machine (trade name: UVF-502S, lamp: UXM 501MD , using SanHisashi made Denki), 1. 5 mW / cm 2 of irradiation power (Ushio Denki made of ultraviolet integration actinometer (trade name: UIT150) and a light receiving sensor (trade name: UVD- S254) to more measurement)) Then, irradiation was performed for 800 seconds to form a graft polymer on the entire surface of the polymerization initiation layer of the substrate B1. Here, the integrated exposure was 1200 mJ.

[0291] その後、攪拌した状態のアセトン中にグラフトポリマーが生成された基板を 5分間浸 漬し、続いて、蒸留水にて洗浄した。 [0291] After that, the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, followed by washing with distilled water.

これにより、ポリマー層を有する基板 B2を得た。  As a result, a substrate B2 having a polymer layer was obtained.

[0292] ポリマー層の物性測定 [0292] Measurement of physical properties of polymer layer

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

•25°C— 50%相対湿度環境下における飽和吸水率： 1. 4質量％ • 25°C— 95 %相対湿度環境下における飽和吸水率： 3. 9質量％ • Saturated water absorption rate at 25 ° C—50% relative humidity: 1.4% by mass • Saturated water absorption at 25 ° C—95% relative humidity: 3.9% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 7. 8質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.8% by mass

•25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置後の表 面接触角： 72. 6度  • 25 ° C—Surface contact angle after dropping 5 ^ L of distilled water in a 50% relative humidity environment and allowing to stand for 15 seconds: 72.6 degrees

[0293] 続いて、このポリマー層を有する基板 B2に対して、実施例 1 1と同様の方法で、 めっき触媒の付与、無電解めつき、及び電気めつきを行った。  [0293] Subsequently, application of a plating catalyst, electroless plating, and electroplating were performed on the substrate B2 having the polymer layer in the same manner as in Example 11.

[0294] 密着性評価 [0294] Adhesion evaluation

得られためっき膜に対して、実施例 1— 1と同様の手法で密着性を評価したところ、 For the obtained plated film, when the adhesion was evaluated in the same manner as in Example 1-1,

90° ピール強度は 0· 68kN/mmであった。 The 90 ° peel strength was 0 · 68kN / mm.

[0295] 金属パターンの形成、及び絶縁信頼性試験 [0295] Formation of metal pattern and insulation reliability test

上記のようにして得られた、めっき膜を有する基板について、実施例 1 1と同様の 手法で、櫛型配線 (金属パターン材料)を形成して絶縁信頼性試験を行ったところ、 配線間の絶縁不良は見られな力、つた。  A substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen.

[0296] 実施例 1 4 [0296] Example 1 4

基板の作製  Fabrication of substrate

25 mの厚みを有するカプトン EN (商品名、東レ ·デュポン (株)製）を基材とした。 この基材の 25°C— 50%相対湿度下での飽和吸水率は、 1. 0質量％であった。 この基材 (樹脂フィルム）の両面に、下記組成の重合開始能を有する絶縁樹脂組成 物をディップ法を用いて塗布し、 100°Cにて 5分間乾燥後、 250°Cで 30分間加熱し て重合開始層（絶縁性の重合開始層）を形成した。なお、重合開始層の 25°C— 50 %相対湿度下での飽和吸水率は、 1. 2質量％であった。  The base material was Kapton EN (trade name, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 m. The saturated water absorption of this base material at 25 ° C.-50% relative humidity was 1.0% by mass. An insulating resin composition having the following polymerization initiating ability is applied to both surfaces of this substrate (resin film) using the dipping method, dried at 100 ° C for 5 minutes, and then heated at 250 ° C for 30 minutes. Thus, a polymerization initiation layer (insulating polymerization initiation layer) was formed. The saturated water absorption rate of the polymerization initiation layer at 25 ° C.-50% relative humidity was 1.2% by mass.

得られた基板を基板 C1とした。この基板 C1の表面凹凸を（Ra)を ISO 4288 (1996) の Raに基づき、サーフコム 3000A (商品名、東京精密（株)製）を用いて測定した所 、 0. 1 μ mであつに。  The obtained substrate was designated as substrate C1. The surface roughness (Ra) of this substrate C1 was measured with Surfcom 3000A (trade name, manufactured by Tokyo Seimitsu Co., Ltd.) based on Ra of ISO 4288 (1996).

[0297] 重合開始能を含有する絶縁性組成物 [0297] Insulating composition containing polymerization initiating ability

ポリイミド前駆体 (ポリアミック酸）の合成  Synthesis of polyimide precursor (polyamic acid)

窒素下にて、 N メチルピロリドン（30ml)中に 4, 4 'ージァミノフエニルエーテル（5 . 75g : 28. 7mmol)を溶解させ、室温にて約 30分間攪拌した。この溶液に 3, 3 '、4 , 4"一べンゾフエノンテトラカルボン酸二無水物（9. 25g : 28. 7mmol)を 0°Cにて加 え 5時間攪拌した。反応液を再沈し、重合開始能を含有するポリイミド前駆体 (ポリア ミック酸）を得た。 GPC (Gel Permeation Chromatography)による分子量（Mw)は 2· 8 万であった。また、更に1 H— NMR、 FT— IRによりその構造を確認した。 Under nitrogen, 4,4′-diaminophenyl ether (5.75 g: 28.7 mmol) was dissolved in N-methylpyrrolidone (30 ml) and stirred at room temperature for about 30 minutes. 3, 3 ', 4 in this solution , 4 "monobenzophenone tetracarboxylic dianhydride (9.25 g: 28.7 mmol) was added at 0 ° C and stirred for 5 hours. The reaction solution was reprecipitated and polyimide containing polymerization initiating ability. The precursor (polyamic acid) was obtained, and the molecular weight (Mw) by GPC (Gel Permeation Chromatography) was 280,000, and the structure was further confirmed by 1 H-NMR and FT-IR.

得られたポリイミド前駆体を N, N—ジメチルァセトアミド（DMAc、和光純薬 (株）社 製）に溶かし、 10質量％の溶液とした。  The obtained polyimide precursor was dissolved in N, N-dimethylacetamide (DMAc, manufactured by Wako Pure Chemical Industries, Ltd.) to give a 10% by mass solution.

[0298] ポリマー層の形成 [0298] Formation of polymer layer

塗布溶液の調製  Preparation of coating solution

前記重合性基及び相互作用性基を有するポリマー A: 10. 5質量部、メチルェチル ケトン（ΜΕΚ) 73· 3質量部、メタノーノレ 33. 9質量部、及び Ν, Ν—ジメチルァセトァ ミド 4. 8質量部を混合攪拌し、塗布溶液を調製した。  Polymer A having Polymerizable Group and Interactive Group A: 10.5 parts by mass, 7-3 parts by mass of methyl ethyl ketone (部), 33.9 parts by mass of methanol, and 4.8 parts by mass of Ν, Ν-dimethylacetamide Were mixed and stirred to prepare a coating solution.

[0299] グラフトポリマーの生成 [0299] Formation of graft polymer

調製された塗布溶液を、ディップ法を用いて前記基板 C1の両面の重合開始層上 に、厚さ 1 mになるように塗布し、 80°Cにて 30分乾燥した後、三永電機製の UV露 光機（商品名： UVF— 502S、ランプ： UXM— 501MD)を用い、 1. 5mW/cm2の 照射パワー（ゥシォ電機製の紫外線積算光量計（商品名： UIT150)及び受光センサ 一（商品名： UVD— S254)により測定)）にて、 660秒間照射させて、基板 C1の重合 開始層にグラフトポリマーを生成させた。ここで、積算露光量は 990mJであった。 The prepared coating solution was applied on the polymerization initiation layers on both sides of the substrate C1 to a thickness of 1 m using the dipping method, dried at 80 ° C for 30 minutes, and then manufactured by Mitsunaga Electric. UV exposure machine (trade name: UVF-502S, lamp: UXM-501MD) of 1.5mW / cm 2 irradiation power (Usio's UV integrated light meter (trade name: UIT150) and light receiving sensor (Trade name: measured by UVD-S254)) for 660 seconds to produce a graft polymer on the polymerization initiation layer of the substrate C1. Here, the integrated exposure was 990 mJ.

[0300] その後、攪拌した状態のアセトン中にグラフトポリマーが生成された基板を 5分間浸 漬し、続いて、蒸留水にて洗浄した。 [0300] Thereafter, the substrate on which the graft polymer was produced was immersed in stirred acetone for 5 minutes, followed by washing with distilled water.

これにより、厚み 0. 8 mのポリマー層を両面に有する基板 C2を得た。  As a result, a substrate C2 having a polymer layer with a thickness of 0.8 m on both sides was obtained.

[0301] ポリマー層の物性測定 [0301] Measurement of physical properties of polymer layer

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

•25°C— 50%相対湿度環境下における飽和吸水率： 1. 2質量％  • Saturated water absorption rate at 25 ° C—50% relative humidity: 1.2% by mass

•25°C— 95%相対湿度環境下における飽和吸水率： 3. 4質量％  • Saturated water absorption at 25 ° C—95% relative humidity: 3.4% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 7. 5質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.5% by mass

•25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置後の表 面接触角： 70. 3度 • 25 ° C—Table after dropping 15 mL of distilled water in a 50% relative humidity environment. Surface contact angle: 70. 3 degrees

[0302] めっき触媒の付与 [0302] Application of plating catalyst

ポリマー層を有する基板 C2を、硝酸パラジウムの 1 %アセトン溶液に、 30分間浸漬 した後、アセトンに浸漬して洗浄した。  The substrate C2 having the polymer layer was immersed in 1% acetone solution of palladium nitrate for 30 minutes and then immersed in acetone for cleaning.

続いて、 1 %ジメチルポラン一水/メタノール (水/メタノール = 1/3)混合溶液に 、ポリマー層を有する基板 B2を 15分浸漬させた後、アセトンに浸漬し洗浄を行った。  Subsequently, the substrate B2 having the polymer layer was immersed in a mixed solution of 1% dimethylporane / water / methanol (water / methanol = 1/3) for 15 minutes, and then immersed in acetone for cleaning.

[0303] 無電解めつき [0303] Electroless plating

上記のようにして、めっき触媒が付与されたポリマー層を有する基板 C2に対し、上 記実施例 1 1と同じ無電解めつき浴を用い、 60°Cで 5分間、無電解めつきを行った 。得られた両面の無電解銅めつき膜の厚みはいずれも 0· 3 mであった。  As described above, the substrate C2 having a polymer layer provided with a plating catalyst was subjected to electroless plating at 60 ° C. for 5 minutes using the same electroless plating bath as in Example 11 above. The The thickness of the obtained electroless copper plating film on both sides was 0 · 3 m.

[0304] 電気めつき [0304] Electric plating

続いて、無電解銅めつき膜を給電層として、上記実施例 1 1と同じ組成の電気銅 めっき浴を用い、 3A/dm2の条件で、電気めつきを 20分間行った。得られた両面の 電気銅めつき膜の厚みはいずれも 18 mであった。 Subsequently, electroplating was performed for 20 minutes under the condition of 3 A / dm 2 using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the same composition as in Example 11 above. The thicknesses of both sides of the obtained copper electroplating film were 18 m.

[0305] 密着性評価 [0305] Adhesion evaluation

得られためっき膜に対して、実施例 1 1と同様に、 5mm幅について、引張強度 10 mm/minにて、 90° ピール強度の測定を行ったところ、 0. 68kN/mであった。  The obtained plated film was measured for a 90 ° peel strength at a tensile strength of 10 mm / min for a width of 5 mm in the same manner as in Example 11. The result was 0.668 kN / m.

[0306] 金属パターンの形成、及び絶縁信頼性試験 [0306] Formation of metal pattern and insulation reliability test

上記のようにして得られた、めっき膜を有する基板について、実施例 1 1と同様の 方法を用いて櫛型配線 (金属パターン)を形成した。  Comb wiring (metal pattern) was formed on the substrate having the plating film obtained as described above using the same method as in Example 11.

その後、この櫛型配線を用いて、実施例 1 1と同様の方法で、絶縁信頼性試験を 行ったところ、配線間の絶縁不良は見られなかった。  Thereafter, an insulation reliability test was performed using this comb-like wiring in the same manner as in Example 11. As a result, no insulation failure was found between the wirings.

[0307] 実施例 1 5 [0307] Example 1 5

実施例 1 1にお!/、て、ポリマー層を形成する際に用いた重合性基及び相互作用 性基を有するポリマー Aを、以下の方法で合成された重合性基及び相互作用性基を 有するポリマー Cに代え、更に、露光条件を、 10mW/cm2の照射パワーで 100秒 間照射することに変更した以外は、実施例 1—1と同様にして、ポリマー層を形成した 。ここで、積算露光量は lOOOmJであった。 これにより、ポリマー層を有する基板 A4を得た。 Example 1 In 1 /, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was converted into a polymerizable group and an interactive group synthesized by the following method. A polymer layer was formed in the same manner as in Example 1-1, except that the exposure condition was changed to irradiation with 100 mW / cm 2 irradiation power for 100 seconds instead of the polymer C having. Here, the integrated exposure was lOOOmJ. As a result, a substrate A4 having a polymer layer was obtained.

なお、ポリマー層を形成する際に、積算露光量を 500mJにした場合であっても、同 様のポリマー層が形成することが分力、つた。  When forming the polymer layer, it was possible to form a similar polymer layer even when the cumulative exposure was 500 mJ.

[0308] 重合性基及び相互作用性基を有するポリマー Cの合成  [0308] Synthesis of Polymer C Having Polymerizable Group and Interactive Group

ヒドロキシェチルアタリレートの市販品（東京化成（株）製） 200mLを水 600mLに溶 解した。得られた水溶液に酢酸ェチル 400mLを加え、油層を分離した。次に、塩化 ナトリウム（和光純薬 (株)製） 100gを水層に溶解させ、その後、酢酸ェチル 200mL を用いて 2回抽出を行った。その後、抽出物を無水硫酸マグネシウムで乾燥し、 p—メ トキシハイドロキノンを 0. 04g添カロし、酢酸ェチルを適度に減圧留去させた。減圧留 去後に、 NMRで確認すると酢酸ェチルが 6. 5質量％残存していた。  200 mL of a commercial product of hydroxyethyl acrylate (Tokyo Kasei Co., Ltd.) was dissolved in 600 mL of water. To the obtained aqueous solution, 400 mL of ethyl acetate was added, and the oil layer was separated. Next, 100 g of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in the aqueous layer, and then extracted twice with 200 mL of ethyl acetate. Thereafter, the extract was dried over anhydrous magnesium sulfate, added with 0.04 g of p-methoxyhydroquinone, and ethyl acetate was distilled off under reduced pressure. After distillation under reduced pressure, it was confirmed by NMR that 6.5% by mass of ethyl acetate remained.

また、液体クロマトグラフィー（HPLC)にてヒドロキシェチルアタリレートの市販品中 の 2官能アタリレートの含有量を測定すると 0. 28質量％であったが、上記のように精 製したものを測定すると、 2官能アタリレートの含有量は検出限界以下であった。  In addition, when the content of bifunctional atarylate in the commercially available product of hydroxyethyl acrylate was measured by liquid chromatography (HPLC), it was 0.28% by mass, but it was measured as purified above. Then, the content of the bifunctional acrylate was below the detection limit.

[0309] 500mLの 3つ口フラスコに N—メチルピロリドンを 20mL、上述の方法で精製された ヒドロキシェチノレアタリレート 2. 32g、シァノエチノレアタリレート 10. Olgを人れ、 75°C に昇温し、その中に、 V— 601 (前述）：0. 23g、及び N—メチルピロリドン 5mLの混 合液を 1時間かけて滴下した。滴下終了後 1時間後に、 80°Cに昇温し 1時間反応さ せた。  [0309] 20 mL of N-methylpyrrolidone in a 500 mL three-necked flask, 2.32 g of hydroxyethinorea talelate purified by the above method, 10. The mixture was added dropwise over 1 hour with a mixture of V-601 (described above): 0.23 g and N-methylpyrrolidone 5 mL. One hour after the completion of the dropwise addition, the temperature was raised to 80 ° C. and reacted for 1 hour.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 29g、ジブチルチンジラ ゥレート 0. 29g、力レンズ AOI (商品名、昭和電工（株）製） 18. 56g、及び N—メチル ピロリドン（SP値： 22. 94MPa1/2) 19gを加え、 55°C、 6時間反応を行った。その後、 反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反応終了後、水で再 沈を行い、固形物を取り出し、重合性基及び相互作用性基を有するポリマー Cを 25g 得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, power lens AOI (trade name, manufactured by Showa Denko KK) 18.56 g, and N-methylpyrrolidone (SP value: 22) 94 MPa 1/2 ) 19 g was added and the reaction was carried out at 55 ° C for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 25 g of polymer C having a polymerizable group and an interactive group was obtained.

[0310] 構造の同定 [0310] Structural identification

合成した重合性基及び相互作用性基を有するポリマー Cを重 DMSO (ジメチルス ルホキシド）に溶解させ、 300MHzの NMR (商品名： AV— 300、ブルカー製）にて 測定を行った。シァノ基含有ユニットに相当するピークが 4. 3-4. 05ppm(2H分）、 2. 9-2. 8ppm(2H分）、 2· 5— 1· 3ppm(3H分）にブロードに観察され、重合性 基含有ユニットに相当するピークが 7· 2-7. 3ppm(lH分）、 6· 4— 6· 3ppm(lH 分）、 6. 2-6. lppm(lH分）、 6. 0— 5. 9ppm(lH分）、 4. 3— 4. 05ppm(6H分 )、 3. 3-3. 2ppm(2H分）、 2. 5-1. 3ppm(3H分） ίこフ、、ロード こ観察され、重合 性基含有ユニット：シァノ基含有ユニット = 20： 80 (mol比）であることが分力、つた。 The synthesized polymer C having a polymerizable group and an interactive group was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). The peak corresponding to the cyano group-containing unit is 4.3-4. 05 ppm (2H min) 2. 9-2. Broadly observed at 8ppm (2H min), 2 · 5—1.3ppm (3H min), and peaks corresponding to polymerizable group-containing units are 7 · 2-7.3ppm (lH min) , 6 · 4– 6 · 3 ppm (lH min), 6.2-6. Lppm (lH min), 6.0 — 5.9 ppm (lH min), 4.3 — 4.05 ppm (6H min), 3 3-3. 2ppm (2H min.), 2. 5-1. 3ppm (3H min.) Rough, load, polymerizable group-containing unit: cyano group-containing unit = 20: 80 (mol ratio) It was a component, to be.

[0311] 分子量の測定  [0311] Measurement of molecular weight

合成した重合性基及び相互作用性基を有するポリマー Cをテトラヒドロフラン (THF )に溶解させ、高速 GPC (商品名、 HLC— 8220GPC、東ソー製）を用いて分子量の 測定を行った。その結果、 23. 75分にピークが現れ、ポリスチレン換算で Mw= 220 00(Mw/Mn = 2. 1)であることが分かった。  The synthesized polymer C having a polymerizable group and an interactive group was dissolved in tetrahydrofuran (THF), and the molecular weight was measured using high-speed GPC (trade name, HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23.75 minutes, and it was found that Mw = 2220 (Mw / Mn = 2.1) in terms of polystyrene.

[0312] ポリマー層の物性測定  [0312] Measurement of physical properties of polymer layer

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

•25°C— 50%相対湿度環境下における飽和吸水率： 1. 3質量％  • 25 ° C—Saturated water absorption in 50% relative humidity environment: 1.3% by mass

• 25°C— 95 %相対湿度環境下における飽和吸水率： 3. 5質量％  • Saturated water absorption at 25 ° C—95% relative humidity: 3.5% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 8. 3質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 8.3 mass%

•25°C— 50%相対湿度環境下において、蒸留水 5^Lを滴下し、 15秒静置後の表 面接触角： 71. 6度  • 25 ° C-Surface contact angle after dropping 5 ^ L of distilled water in a 50% relative humidity environment and standing for 15 seconds: 71.6 degrees

[0313] 続いて、このポリマー層を有する基板 A4に対して、実施例 1 1と同様の方法で、 めっき触媒の付与、無電解めつき、及び電気めつきを行った。更に、 170°Cで 30分 の後加熱を行った。  [0313] Subsequently, application of a plating catalyst, electroless plating, and electroplating were performed on the substrate A4 having this polymer layer in the same manner as in Example 11. Furthermore, post-heating was performed at 170 ° C for 30 minutes.

[0314] 密着性評価 [0314] Adhesion evaluation

得られためっき膜に対して、実施例 1— 1と同様の手法で密着性を評価したところ、 For the obtained plated film, when the adhesion was evaluated in the same manner as in Example 1-1,

90° ピーノレ強度は 0· 75kN/mmであった。 The 90 ° pinole strength was 0 · 75kN / mm.

[0315] 金属パターンの形成、及び絶縁信頼性試験 [0315] Formation of metal pattern and insulation reliability test

上記のようにして得られた、めっき膜を有する基板について、実施例 1 1と同様の 手法で、櫛型配線 (金属パターン材料)を形成して絶縁信頼性試験を行ったところ、 配線間の絶縁不良は見られな力、つた。 [0316] 実施例 1 6 A substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen. [0316] Example 1 6

実施例 1 1にお!/、て、ポリマー層を形成する際に用いた重合性基及び相互作用 性基を有するポリマー Aを、以下の方法で合成された重合性基及び相互作用性基を 有するポリマー Dに代え、更に、露光条件を、 10mW/cm2の照射パワーで 100秒 間照射することに変更した以外は、実施例 1—1と同様にして、ポリマー層を形成した 。ここで、積算露光量は lOOOmJであった。 Example 1 In 1 /, the polymer A having a polymerizable group and an interactive group used in forming the polymer layer was converted into a polymerizable group and an interactive group synthesized by the following method. A polymer layer was formed in the same manner as in Example 1-1, except that the exposure condition was changed to irradiation with 100 mW / cm 2 irradiation power for 100 seconds instead of the polymer D having. Here, the integrated exposure was lOOOmJ.

これにより、ポリマー層を有する基板 A5を得た。  As a result, a substrate A5 having a polymer layer was obtained.

なお、ポリマー層を形成する際に、積算露光量を 500mJにした場合であっても、同 様のポリマー層が形成することが分力、つた。  When forming the polymer layer, it was possible to form a similar polymer layer even when the cumulative exposure was 500 mJ.

[0317] 重合性基及び相互作用性基を有するポリマー Dの合成 [0317] Synthesis of Polymer D with Polymerizable Group and Interactive Group

500mLの 3つ口フラスコにエチレングリコールジアセテートを l lmL入れ、 75°Cに 昇温し、その中に、実施例 1—5に記載の方法で精製されたヒドロキシェチルアタリレ 一卜 1. 39g、シァノエチルアタリレー卜 6. OOg、 V— 601 (前述）： 0. 1382g、及びェ チレングリコールジアセテート l lmLの混合液を 2. 5時間かけて滴下した。滴下終了 後、 80°Cに昇温し 3時間反応させた。  In a 500 mL three-necked flask, add l mL of ethylene glycol diacetate, raise the temperature to 75 ° C., and add hydroxyethyl ateryl purified by the method described in Example 1-5. 39 g, cyanoethyl attareyl salt 6. OOg, V-601 (previously described): 0.1382 g and 1 mL of ethylene glycol diacetate were added dropwise over 2.5 hours. After completion of dropping, the temperature was raised to 80 ° C. and reacted for 3 hours.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 06g、無機ビスマス系ゥ レタン化架橋触媒（商品名：ネオスタン U— 600、 日東化成製） 0. 13g、力レンズ AOI (商品名、昭和電工（株）製） 3· 84g、及びエチレングリコールジアセテート（SP値：2 0. 79MPa1/2) 3. 8gをカロえ、 55。C、 6時間反応を行った。 Ditertiary butyl hydroquinone 0.06g, inorganic bismuth-based urethane cross-linking catalyst (trade name: Neostan U-600, manufactured by Nitto Kasei) 0.13g, power lens AOI (trade name, Showa Denko Co., Ltd.) )) 3 · 8 4 g and ethylene glycol diacetate (SP value: 2 0. 79 MPa 1/2 ) 3. C, reaction was performed for 6 hours.

その後、反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反応終了 後、水で再沈を行い、固形物を取り出し、重合性基及び相互作用性基を有するポリ マー Dを 3g得た。  Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain 3 g of Polymer D having a polymerizable group and an interactive group.

[0318] 構造の同定 [0318] Structural identification

合成した重合性基及び相互作用性基を有するポリマー Dを重 DMSO (ジメチルス ルホキシド）に溶解させ、 300MHzの NMR (商品名： AV— 300、ブルカー製）にて 測定を行った。二トリル基含有ユニットに相当するピークが 4· 3-4. 05ppm(2H分） 、 2. 9- 2. 8ppm(2H分）、 2. 5- 1. 3ppm(3H分）にブロードに観察され、重合性 基含有ユニットに相当するピークが 7· 2- 7. 3ppm (lH分）、 6· 4— 6· 3ppm (lH 分）、 6. 2 - 6. lppm ( lH分）、 6. 0— 5. 9ppm ( lH分）、 4. 3— 4. 05ppm (6H分 )、 3. 3 - 3. 2ppm (2H分）、 2. 5 - 1. 3ppm (3H分） ίこフ、、ロード こ観察され、重合 性基含有ユニット：二トリル基含有ユニット = 21： 79 (mol比）である事が分力、つた。 The synthesized polymer D having a polymerizable group and an interactive group was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). Peaks corresponding to nitrile group-containing units are broadly observed at 4.3-3.05 ppm (2H min), 2.9-1.8 ppm (2H min), 2.5-1.3 ppm (3H min) The peaks corresponding to the polymerizable group-containing units are 7 · 2–7.3 ppm (lH component), 6 · 4– 6 · 3 ppm (lH Min), 6.2-6. lppm (lH min), 6.0—5.9 ppm (lH min), 4.3—4.05 ppm (6H min), 3.3-3.3.2 ppm (2H min) 2.5-1. 3 ppm (3H min.) Ί フ, ロ ー ド ロ ー ド ロ ー ド ロ ー ド 観 察 観 察 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 重合 観 察 観 察 重合 重合 重合 観 察 重合 観 察 観 察 観 察 観 察 2. 2. 2.

[0319] 分子量の測定  [0319] Measurement of molecular weight

合成した重合性基及び相互作用性基を有するポリマー Dを THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。そ の結果、 23· 75分にピークが現れ、ポリスチレン換算で Mw= 84000 (Mw/Mn = 2. 9)であることが分かった。  The synthesized polymer D having a polymerizable group and an interactive group was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23 · 75 minutes and was found to be Mw = 84000 (Mw / Mn = 2.9) in terms of polystyrene.

[0320] ポリマー層の物性測定  [0320] Measurement of polymer layer properties

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

•25°C— 50%相対湿度環境下における飽和吸水率： 1. 2質量％  • Saturated water absorption rate at 25 ° C—50% relative humidity: 1.2% by mass

• 25°C— 95 %相対湿度環境下における飽和吸水率： 3. 6質量％  • Saturated water absorption at 25 ° C—95% relative humidity: 3.6% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 7. 7質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 7.7% by mass

•25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置後の表 面接触角： 70. 8度  • 25 ° C—Surface contact angle after dripping 5 ^ L of distilled water in a 50% relative humidity environment and allowing to stand for 15 seconds: 70.8 degrees

[0321] 続いて、このポリマー層を有する基板 A5に対して、実施例 1 1と同様の方法で、 めっき触媒の付与、無電解めつき、及び電気めつきを行った。更に、 170°Cで 30分 の後加熱を行った。  [0321] Subsequently, application of a plating catalyst, electroless plating, and electroplating were performed on the substrate A5 having this polymer layer in the same manner as in Example 11. Furthermore, post-heating was performed at 170 ° C for 30 minutes.

[0322] 密着性評価 [0322] Adhesion evaluation

得られためっき膜に対して、実施例 1— 1と同様の手法で密着性を評価したところ、 90° ピーノレ強度は 0· 76kN/mmであった。  When the adhesion of the obtained plated film was evaluated by the same method as in Example 1-1, the 90 ° pinole strength was 0 · 76 kN / mm.

[0323] 金属パターンの形成、及び絶縁信頼性試験 [0323] Formation of metal pattern and insulation reliability test

上記のようにして得られた、めっき膜を有する基板について、実施例 1 1と同様の 手法で、櫛型配線 (金属パターン材料)を形成して絶縁信頼性試験を行ったところ、 配線間の絶縁不良は見られな力、つた。  A substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen.

[0324] 実施例 1 7 [0324] Example 1 7

実施例 1 1にお!/、て、ポリマー層を形成する際に用いた重合性基及び相互作用 性基を有するポリマー Aを、以下の方法で合成された重合性基及び相互作用性基を 有するポリマー Eに代え、更に、露光条件を、 10mW/cm2の照射パワーで 100秒 間照射することに変更した以外は、実施例 1—1と同様にして、ポリマー層を形成した 。ここで、積算露光量は lOOOmJであった。 Example 1 In 1! /, The polymerizable group and interaction used in forming the polymer layer The polymer A having a reactive group is replaced with the polymer E having a polymerizable group and an interactive group synthesized by the following method, and the exposure condition is irradiated for 100 seconds with an irradiation power of 10 mW / cm 2. A polymer layer was formed in the same manner as in Example 1-1, except for changing to. Here, the integrated exposure was lOOOmJ.

これにより、ポリマー層を有する基板 A6を得た。  As a result, a substrate A6 having a polymer layer was obtained.

なお、ポリマー層を形成する際に、積算露光量を 500mJにした場合であっても、同 様のポリマー層が形成することが分力、つた。  When forming the polymer layer, it was possible to form a similar polymer layer even when the cumulative exposure was 500 mJ.

[0325] 重合性基及び相互作用性基を有するポリマー Eの合成 [0325] Synthesis of Polymer E with Polymerizable Group and Interactive Group

500mLの 3つ口フラスコにエチレングリコールジアセテートを 10mL入れ、 80°Cに 昇温し、その中に、実施例 1—5に記載の方法で精製されたヒドロキシェチルアタリレ ート 3. 72g、シァノエチルアタリレート 16. 01g、 V— 601 (前述）： 0. 3684g、及びェ チレングリコールジアセテート 10mLの混合液を 4時間かけて滴下した。滴下終了後 、更に 3時間反応させた。  Place 10 mL of ethylene glycol diacetate in a 500 mL three-necked flask, raise the temperature to 80 ° C, and then add 3.72 g of hydroxyethyl acrylate, purified by the method described in Example 1-5. Then, a mixed solution of 16.01 g of cyanoethyl acrylate and V-601 (described above): 0.3684 g and 10 mL of ethylene glycol diacetate was added dropwise over 4 hours. After completion of dropping, the reaction was further continued for 3 hours.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 16g、ネオスタン U— 6 00 (前述） 0. 32g、力レンズ AOI (商品名、昭和電工（株）製） 9· 6g、及びエチレング リコールジアセテート（SP値：20· 79MPa1/2) 9. 6gを加え、 55°C、 6時間反応を行 つた。その後、反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反応 終了後、水で再沈を行い、固形物を取り出し、重合性基及び相互作用性基を有する ポリマー Eを 18g得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.16 g, neostan U—600 (previously described) 0.32 g, force lens AOI (trade name, manufactured by Showa Denko KK) 9 · 6 g, and ethylene glycol diacetate ( SP value: 20 · 79 MPa 1/2 ) 9. 6 g was added and the reaction was carried out at 55 ° C for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 18 g of polymer E having a polymerizable group and an interactive group was obtained.

[0326] 構造の同定 [0326] Structural identification

合成した重合性基及び相互作用性基を有するポリマー Eを実施例 1 2と同様にし て NMR測定を行ったところ、重合性基含有ユニット:二トリル基含有ユニット = 23 : 7 7 (mol比）であることが分かった。  NMR measurement was performed on the synthesized polymer E having a polymerizable group and an interactive group in the same manner as in Example 12. The polymerizable group-containing unit: nitrile group-containing unit = 23: 77 (mol ratio) It turns out that.

[0327] 分子量の測定 [0327] Measurement of molecular weight

合成した重合性基及び相互作用性基を有するポリマー Eを THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。そ の結果、 23· 75分にピークが現れ、ポリスチレン換算で Mw= 66000 (Mw/Mn = 2. 8)であることが分かった。 [0328] ポリマー層の物性測定 The synthesized polymer E having a polymerizable group and an interactive group was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23 · 75 minutes and was found to be Mw = 66000 (Mw / Mn = 2.8) in terms of polystyrene. [0328] Measurement of physical properties of polymer layer

得られたポリマー層の物性について前述の方法で測定した。結果は以下の通りで ある。  The physical properties of the obtained polymer layer were measured by the method described above. The results are as follows.

•25°C— 50%相対湿度環境下における飽和吸水率： 1. 2質量％  • Saturated water absorption rate at 25 ° C—50% relative humidity: 1.2% by mass

•25°C— 95%相対湿度環境下における飽和吸水率： 3. 4質量％  • Saturated water absorption at 25 ° C—95% relative humidity: 3.4% by mass

• 100°C煮沸水に 1時間浸漬した後の吸水率： 8. 1質量％  • Water absorption after immersion in boiling water at 100 ° C for 1 hour: 8.1% by mass

•25°C— 50%相対湿度環境下において、蒸留水 5 ^ Lを滴下し、 15秒静置後の表 面接触角： 70. 0度  • 25 ° C—Surface contact angle after dripping 5 ^ L of distilled water in a 50% relative humidity environment and allowing to stand for 15 seconds: 70.0 degrees

[0329] 続いて、このポリマー層を有する基板 A6に対して、実施例 1 1と同様の方法で、 めっき触媒の付与、無電解めつき、及び電気めつきを行った。更に、 170°Cで 30分 の後加熱を行った。  [0329] Subsequently, application of a plating catalyst, electroless plating, and electroplating were performed on the substrate A6 having this polymer layer in the same manner as in Example 11. Furthermore, post-heating was performed at 170 ° C for 30 minutes.

[0330] 密着性評価 [0330] Adhesion evaluation

得られためっき膜に対して、実施例 1— 1と同様の手法で密着性を評価したところ、 90° ピーノレ強度は 0· 76kN/mmであった。  When the adhesion of the obtained plated film was evaluated by the same method as in Example 1-1, the 90 ° pinole strength was 0 · 76 kN / mm.

[0331] 金属パターンの形成、及び絶縁信頼性試験 [0331] Formation of metal pattern and insulation reliability test

上記のようにして得られた、めっき膜を有する基板について、実施例 1 1と同様の 手法で、櫛型配線 (金属パターン材料)を形成して絶縁信頼性試験を行ったところ、 配線間の絶縁不良は見られな力、つた。  A substrate having a plating film obtained as described above was subjected to an insulation reliability test after forming a comb-shaped wiring (metal pattern material) in the same manner as in Example 11. Insufficient insulation was a power not seen.

[0332] 実施例 1 8 [0332] Example 1 8

実施例 1 1で作製した、重合開始層が形成された基板 A1を用い、以下のようにし て金属パターン材料を作製した。  Using the substrate A1 with a polymerization initiation layer formed in Example 11 1, a metal pattern material was prepared as follows.

[0333] ポリマー層の形成 [0333] Formation of polymer layer

実施例 1—1と同様に、重合性基及び相互作用性基を有するポリマー Aを用いた塗 布溶液を調製した。  In the same manner as in Example 1-1, a coating solution using Polymer A having a polymerizable group and an interactive group was prepared.

[0334] グラフトポリマーのパターン形成 [0334] Pattern formation of graft polymer

調製された塗布溶液を、スピンコートにて前記基板 A1の重合開始層上に、厚さ 1 μ mになるように、スピンコート法により塗布し、 80°Cにて 5分乾燥した後、三永電機製 の UV露光機（商品名： UVF— 502S、ランプ： UXM— 501MD)を用い、 10mW/ cm2の照射パワー（ゥシォ電機製の紫外線積算光量計（商品名： UIT150)及び受光 センサー（商品名： UVD— S254)により測定)）にて、 100秒間照射した。その際に、 塗布溶液を塗布乾燥した基板 A1上に、幅 5mm、長さ 50mmのパターンが 0. lmm 間隔で並んだマスク A、又は、ライン'アンド 'スペース = 100 ^ 111/ 100 ^ mくし型配 線のマスク Bを置いて露光することで、基板 A1の重合開始層上に対してパターン状 にグラフトポリマーを生成させた。ここで、積算露光量は lOOOmJであった。 The prepared coating solution was applied by spin coating to a thickness of 1 μm on the polymerization initiation layer of the substrate A1 by spin coating, dried at 80 ° C. for 5 minutes, 10mW / using a UV exposure machine (product name: UVF-502S, lamp: UXM-501MD) manufactured by Electric Electric Irradiation was performed for 100 seconds with an irradiation power of cm 2 (measured with a UV integrated light meter (trade name: UIT150) and a light receiving sensor (trade name: UVD-S254) manufactured by Usio Denki). At that time, mask A or line 'and' space = 100 ^ 111/100 ^ m with a pattern of 5 mm in width and 50 mm in length arranged at 0.1 mm intervals on substrate A1 coated with the coating solution and dried. By placing and exposing a mask B of mold wiring, a graft polymer was formed in a pattern on the polymerization initiation layer of the substrate A1. Here, the integrated exposure was lOOOmJ.

[0335] その後、攪拌した状態のァセトニトリル中にグラフトポリマーが生成された基板を 5分 間浸漬し、続いて、蒸留水にて洗浄した。 [0335] Thereafter, the substrate on which the graft polymer was formed was immersed in agitated acetonitrile for 5 minutes, and then washed with distilled water.

これにより、幅 5mm、長さ 50mmのパターン形状で、厚み 0· 5 mのポリマー層を 有する基板 A7 (マスク Aを用いたもの）、 A8 (マスク Bを用いたもの）を得た。  As a result, substrates A7 (using mask A) and A8 (using mask B) having a pattern shape of 5 mm in width and 50 mm in length and having a polymer layer with a thickness of 0.5 m were obtained.

[0336] ポリマー層の物性測定 [0336] Measurement of physical properties of polymer layer

得られたポリマー層の各物性は実施例 1 1と同様であった。  The physical properties of the obtained polymer layer were the same as in Example 11.

[0337] めっき触媒の付与 [0337] Application of plating catalyst

ポリマー層を有する基板 A7を、硝酸パラジウムの 0. 1重量％アセトン溶液に、 30 分間浸漬した後、アセトンに浸漬して洗浄した。  The substrate A7 having a polymer layer was immersed in a 0.1 wt% acetone solution of palladium nitrate for 30 minutes, and then immersed in acetone for cleaning.

[0338] 無電解めつき [0338] Electroless plating

上記のようにして、めっき触媒が付与されたポリマー層を有する基板 A7に対し、下 記組成の無電解めつき浴を用い、 60°Cで 15分間、無電解めつきを行った。得られた 無電解銅めつき膜の厚みは 0· 50 mであった。  As described above, the substrate A7 having a polymer layer provided with a plating catalyst was subjected to electroless plating at 60 ° C. for 15 minutes using an electroless plating bath having the following composition. The thickness of the obtained electroless copper plating film was 0 · 50 m.

[0339] 無電解めつき浴の組成  [0339] Composition of electroless bath

，蒸留水 1700g  , Distilled water 1700g

'硫酸銅 18. lg  'Copper sulfate 18. lg

'エチレンジァミン四酢酸.2ナトリウム塩 54. Og  'Ethylenediamine tetraacetic acid.2 sodium salt 54. Og

•ポリオキシエチレングリコール（分子量 1000) 0. 18g  • Polyoxyethylene glycol (molecular weight 1000) 0.18g

.2, 2 'ビビリジノレ ―. 8mg  .2, 2 'Bibiridinole ―. 8mg

• 10%エチレンジァミン水溶液 7. lg • 10% ethylenediamine aqueous solution 7. lg

Figure imgf000101_0001
Figure imgf000101_0001

以上の組成のめっき浴の pHを、水酸化ナトリウム及び硫酸で 12. 5 (60°C)に調整 した。 Adjust the pH of the plating bath with the above composition to 12.5 (60 ° C) with sodium hydroxide and sulfuric acid. did.

[0340] 電気めつき  [0340] Electric plating

続いて、無電解銅めつき膜を給電層として、実施例 1—1と同様の方法で、基板 A7 には厚み 18 m、基板 A8には厚み 10 μ mの電気銅めつき膜となるように電気めつ きを行った。  Next, using the electroless copper plating film as the power feeding layer, the same method as in Example 1-1 was used to form an electrolytic copper plating film with a thickness of 18 m on substrate A7 and a thickness of 10 μm on substrate A8. Electricity was turned on.

電気めつき終了後、 100°Cで 30分、 170°Cで 1時間ベータを行った。  After the completion of electric plating, beta was performed at 100 ° C for 30 minutes and at 170 ° C for 1 hour.

[0341] 密着性評価 [0341] Adhesion evaluation

上記のようにして得られた、基板 A7の金属パターンめっき膜に対して、引張試験機 ( (株）ェ一.アンド 'デー製、 RTM—100)を用いて、引張強度 10mm/minにて、 9 0° ピール強度の測定を行ったところ、 0. 65kN/mmであった。  For the metal pattern plating film of the substrate A7 obtained as described above, using a tensile testing machine (RTM-100, manufactured by Ei-and-D, Inc.) at a tensile strength of 10 mm / min. The 90 ° peel strength was measured and found to be 0.65 kN / mm.

[0342] 絶縁信頼性試験 [0342] Insulation reliability test

上記のようにして得られた、基板 A8の金属パターンについて、実施例 1 1の方法 に準じた手法で、絶縁信頼性試験を行ったところ、配線間（金属パターン間）の絶縁 不良は見られなかった。  When the insulation reliability test was performed on the metal pattern of the substrate A8 obtained as described above by the method according to the method of Example 11 1, there was an insulation failure between the wires (between the metal patterns). There wasn't.

[0343] 実施例 2— 1 [0343] Example 2-1

合成例:本発明の二トリル基含有重合性ポリマー Aの合成  Synthesis example: synthesis of nitrile group-containing polymerizable polymer A of the present invention

1000mlの三口フラスコに、 N メチルピロリドン 35gを入れ、窒素気流下、 75°Cま で加熱した。そこへ、 2 ヒドロキシェチルアタリレート（市販品、東京化成製） 6. 60g 、 2 シァノエチノレアタリレート 28· 4g、及び V— 601 (前述） 0· 65gの N メチノレピロ リドン 35g溶液を、 2. 5時間かけて滴下した。滴下終了後、 80°Cまで加熱し、更に 3 時間撹拌した。その後、室温まで、反応溶液を冷却した。  In a 1000 ml three-necked flask, 35 g of N-methylpyrrolidone was placed and heated to 75 ° C. under a nitrogen stream. Then, 2 hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.) 2. Dropped over 5 hours. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 29g、ジブチルチンジラ ゥレート 0. 29g、力レンズ AOI (商品名、昭和電工（株）製） 18. 56g、及び N メチル ピロリドン 19gを加え、 55°C、 6時間反応を行った。その後、反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反応終了後、水で再沈を行い、固形物を取り 出し、本発明の二トリル基含有重合性ポリマー Aを 25g得た。  Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, power lens AOI (trade name, manufactured by Showa Denko KK) 18.56 g and N methyl pyrrolidone 19 g are added to the above reaction solution, 55 ° C, reaction was performed for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water to take out a solid, and 25 g of the nitrile group-containing polymerizable polymer A of the present invention was obtained.

[0344] 構造の同定 [0344] Structural identification

合成した二トリル基含有重合性ポリマー Aを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに 相当するピーク力 3-4. 05ppm (2H分）、 2. 9— 2. 8ppm (2H分）、 2. 5— 1. 3 ppm (3H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 2 - 7. 3ppm (lH分）、 6. 4— 6. 3ppm (lH分）、 6. 2— 6. lppm (lH分）、 6. 0— 5 . 9ppm (lH分）、 4. 3— 4. 05ppm (6H分）、 3. 3— 3. 2ppm (2H分）、 2. 5— 1. 3 ppm (3H分）にブロードに観察され、重合性基含有ユニット:二トリル基含有ユニット = 23 : 77 (mol比）であることが分かった。 The synthesized nitrile group-containing polymerizable polymer A is dissolved in heavy DMSO, and 300MHz N Measurement was performed with MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing unit 3-4. 05ppm (2H min), 2.9—2.8 ppm (2H min), 2.5—1.3 ppm (3H min) Peaks corresponding to polymerizable group-containing units are 7.2-7. 3 ppm (lH component), 6.4— 6. 3 ppm (lH component), 6.2 — 6. lppm (lH component), 6.0 — 5.9 ppm (lH), 4.3—4.05 ppm (6H), 3.3—3.2 ppm (2H), 2.5—1.3 ppm (3H), It was found that the polymerizable group-containing unit: nitrile group-containing unit = 23: 77 (mol ratio).

[0345] 分子量の測定  [0345] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Aを、 THFに溶解させ、高速 GPC (商品名 ： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 23. 7 5分にピークが現れ、ポリスチレン換算で Mw= 5300 (Mw/Mn= l . 54)であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer A was dissolved in THF, and molecular weight was measured using a high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23.75 minutes, and the component force was Mw = 5300 (Mw / Mn = l.54) in terms of polystyrene.

[0346] 二トリル基含有重合性ポリマー Aの使用態様  [0346] Usage mode of nitrile group-containing polymerizable polymer A

ガラスエポキシ基板上に、電気的絶縁層としてエポキシ系絶縁膜（商品名： GX— 1 3、味の素ファインテクノ社製、膜厚: 45 m)を、加熱、加圧して、真空ラミネーター により 0. 2MPaの圧力で 100°C〜110°Cの条件により接着して、基材 Aを得た。 ついで、基材 Aの上に、下記組成の重合開始剤を含有する絶縁性組成物を厚さ 3 ミクロンになるようにスピンコート法で塗布し、 30°Cにて 1時間放置して溶剤を除去し た後、 140°Cで 30分乾燥して重合開始層（絶縁性の重合開始層）を形成した。  An epoxy insulating film (product name: GX-1 3; Ajinomoto Fine-Techno Co., Ltd., film thickness: 45 m) is heated and pressurized on the glass epoxy substrate as an electrical insulating layer, and 0.2 MPa using a vacuum laminator. The substrate A was obtained by bonding under conditions of 100 ° C. to 110 ° C. Next, an insulating composition containing a polymerization initiator having the following composition was applied onto substrate A by spin coating so as to have a thickness of 3 microns, and left at 30 ° C for 1 hour to remove the solvent. After the removal, it was dried at 140 ° C. for 30 minutes to form a polymerization initiation layer (insulating polymerization initiation layer).

[0347] 重合開始剤を含有する絶縁性組成物  [0347] Insulating composition containing a polymerization initiator

液状ビスフエノール A型エポキシ樹脂（エポキシ当量 176、ジャパンエポキシレジン（ 株)製、商品名：ェピコート 825) 5g、トリァジン構造含有フエノールノポラック樹脂の MEKワニス（大日本インキ化学工業 (株)製、商品名：フエノライト LA— 7052、不揮 発分： 62%、不揮発分のフエノール性水酸基当量： 120) 2g、フエノキシ樹脂 MEKヮ ニス (東都化成 (株)製、商品名： YP— 50EK35、不揮発分：35%) 10. 7g、重合開 始剤として 2—ヒドロキシー4，一（2—ヒドロキシエトキシ）ー2—メチルプロピオフエノン 2. 3g、 MEK5. 3g、 2—ュチノレー 4ーメチノレイミダゾ、一ノレ 0. 053gを混合し、 WL て完全に溶解させて重合開始剤を含有する絶縁性組成物を得た。 [0348] 上記のような重合開始層が形成された後、 180°Cで 30分間硬化処理を実施した。 これにより、基板 A1を得た。この基板 A1の表面凹凸（Rz)は 0. 2〃mであった。 Liquid bisphenol A type epoxy resin (epoxy equivalent 176, manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 825) 5g, MEK varnish of phenolic nopolak resin containing triazine structure (manufactured by Dainippon Ink & Chemicals, Inc., product) Name: Phenolite LA— 7052, Nonvolatile content: 62%, Non-volatile phenolic hydroxyl group equivalent: 120) 2 g, Phenoxy resin MEK ヮ varnish (manufactured by Toto Kasei Co., Ltd., trade name: YP—50EK35, Non-volatile content: 35%) 10.7g, 2-hydroxy-4,1 (2-hydroxyethoxy) -2-methylpropiophenone 2.3g, MEK5.3g, 2-tuccinore 4-methinoreimidazo, 1nore as polymerization initiator 0.53 g was mixed and completely dissolved in WL to obtain an insulating composition containing a polymerization initiator. [0348] After the polymerization initiation layer as described above was formed, a curing treatment was performed at 180 ° C for 30 minutes. Thereby, a substrate A1 was obtained. The surface roughness (Rz) of this substrate A1 was 0.2 mm.

[0349] 塗布溶液の調製  [0349] Preparation of coating solution

前述の合成例で得られた本発明の二トリル基含有重合性ポリマー A: 10. 5質量部 、アセトン 73. 3質量部、メタノール 33. 9質量部、及び N, Nジメチルァセトアミド 4. 8 質量部を混合攪拌し、塗布溶液を調製した。  The nitrile group-containing polymerizable polymer A of the present invention obtained in the above synthesis example: 10.5 parts by mass, acetone 73.3 parts by mass, methanol 33.9 parts by mass, and N, N dimethylacetamide 4. 8 parts by mass were mixed and stirred to prepare a coating solution.

[0350] 露光  [0350] Exposure

調製された塗布溶液を、前記基板 A1の重合開始層上に、厚さ 1 μ mになるように、 スピンコート法により塗布し、 80°Cにて 30分乾燥した後、三永電機製の UV露光機（ 商品名： UVF— 502S、ランプ： UXM— 501MD)を用い、 1. 5mW/cm2の照射パ ヮー（ゥシォ電機製の紫外線積算光量計（商品名： UIT150)及び受光センサー（商 品名： UVD— S254)により測定)）にて、 660秒間照射させて、基板 A1の重合開始 層の全面で、二トリル基含有重合性ポリマー Aを反応させた。 The prepared coating solution was applied onto the polymerization initiation layer of the substrate A1 by a spin coating method so as to have a thickness of 1 μm and dried at 80 ° C. for 30 minutes. UV exposure machine (trade name: UVF- 502S, lamp: UXM- 501MD) using, 1. 5mW / cm 2 of irradiation path Wa (Ushio Denki manufactured accumulated UV actinometer (trade name: UIT150) and a light receiving sensor (quotient Product name: Measured according to UVD—S254))))) for 660 seconds to react the nitrile group-containing polymerizable polymer A on the entire surface of the polymerization initiation layer of the substrate A1.

[0351] その後、攪拌した状態のアセトン中に光硬化層が形成された基板を 5分間浸漬し、 続いて、蒸留水にて洗浄した。 [0351] After that, the substrate on which the photocured layer was formed was immersed in stirred acetone for 5 minutes, and then washed with distilled water.

これにより、ポリマー層を有する基板 A2を得た。  Thereby, a substrate A2 having a polymer layer was obtained.

[0352] めっき触媒の付与 [0352] Application of plating catalyst

ポリマー層を有する基板 A2を、 Pdの 1 %アセトン溶液に、 30分間浸漬した後、ァセ トンに浸漬して洗浄した。  Substrate A2 having a polymer layer was immersed in a 1% acetone solution of Pd for 30 minutes, and then immersed in acetone and washed.

続いて、 1 %ジメチルポラン一水/メタノール (水/メタノール = 1/3)混合溶液を 触媒活性化液 (還元液）として用い、この溶液中に、ポリマー層を有する基板 A2を 15 分浸漬させた後、アセトンに浸漬し洗浄を行った。  Subsequently, a 1% dimethylporane monohydrate / methanol (water / methanol = 1/3) mixed solution was used as a catalyst activation liquid (reducing liquid), and a substrate A2 having a polymer layer was immersed in this solution for 15 minutes. Then, it was immersed in acetone for cleaning.

[0353] 無電解めつき [0353] Electroless plating

上記のようにして、めっき触媒が付与されたポリマー層を有する基板 A2に対し、下 記組成の無電解めつき浴を用い、 60°Cで 5分間、無電解めつきを行った。得られた 無電解銅めつき膜の厚みは 0· 3 mであった。  As described above, electroless plating was carried out at 60 ° C. for 5 minutes using the electroless plating bath having the following composition on the substrate A2 having a polymer layer provided with a plating catalyst. The thickness of the obtained electroless copper plating film was 0.3 m.

[0354] 無電解めつき浴の組成 [0354] Composition of electroless bath

•蒸留水 859g •メタノーノレ 850g • 859g of distilled water • Metanore 850g

'硫酸銅 18. lg  'Copper sulfate 18. lg

'エチレンジァミン四酢酸.2ナトリウム塩 54. Og  'Ethylenediamine tetraacetic acid.2 sodium salt 54. Og

•ポリオキシエチレングリコール（分子量 1000) 0. 18g  • Polyoxyethylene glycol (molecular weight 1000) 0.18g

•2, 2 'ビビリジノレ ―. 8mg  • 2, 2 'bibilidinole-8mg

• 10%エチレンジァミン水溶液 7. lg • 10% ethylenediamine aqueous solution 7. lg

Figure imgf000105_0001
Figure imgf000105_0001

以上の組成のめっき浴の pHを、水酸化ナトリウム及び硫酸で 12. 5 (60°C)に調整 した。  The pH of the plating bath having the above composition was adjusted to 12.5 (60 ° C) with sodium hydroxide and sulfuric acid.

電気めつき  Electricity

続いて、無電解銅めつき膜を給電層として、下記組成の電気銅めつき浴を用い、 3 A/dm2の条件で、電気めつきを 20分間行った。その後、 120°C、 1時間、ベーク処 理を行った。得られた電気銅めつき膜の厚みは 18 mであった。 Subsequently, electroplating was carried out for 20 minutes under the condition of 3 A / dm 2 using an electroless copper plating film with the electroless copper plating film as the power feeding layer. Thereafter, baking was performed at 120 ° C for 1 hour. The thickness of the obtained electrolytic copper plating film was 18 m.

[0356] 電気めつき浴の組成  [0356] Composition of electric bath

'硫酸銅 38g  'Copper sulfate 38g

'硫酸 95g  'Sulfuric acid 95g

•塩酸 lmL  Hydrochloric acid lmL

•カッパーグリーム PCM (商品名、メルテックス（株）製） 3mL  • Copper Grime PCM (trade name, manufactured by Meltex Co., Ltd.) 3mL

•水 500g  • Water 500g

[0357] 金属パターンの形成、及び絶縁信頼性試験  [0357] Formation of metal pattern and insulation reliability test

得られためっき膜表面に、金属パターン (配線パターン）として残すべき領域にエツ チングレジストを形成し、レジストのない領域のめっき膜を、 FeCl /HC1からなるエツ  On the surface of the obtained plating film, an etching resist is formed in a region to be left as a metal pattern (wiring pattern), and a plating film in a region having no resist is formed by etching with FeCl / HC1.

3  Three

チング液により除去した。その後、エッチングレジストを 3%NaOH液からなるアルカリ 剥離液にて除去し、ソルダーレジストでカバーして、ライン'アンド 'スペース = 100〃 m/10011 mの線間絶縁信頼性を測定するための櫛形配線 (金属パターン材料）を 形成した。  It was removed with a ching solution. After that, the etching resist is removed with an alkaline stripping solution consisting of 3% NaOH solution, covered with a solder resist, and comb-shaped for measuring the insulation reliability between lines 'and' space = 100〃m / 10011 m. Wiring (metal pattern material) was formed.

この櫛形配線を、 £3?£じ製^1八3丁試験機（八^[1 1503— 25)にて、 125°C— 8 5%相対湿度（未飽和）、印加電圧 10V、 2気圧下で 200時間放置させた所、配線間 の絶縁不良は見られなかった。 This comb-shaped wire is connected to a £ 3? £ ^ 1-8 3-cutter (8 ^ [1 1503-25]), 125 ° C—85% relative humidity (unsaturated), applied voltage 10 V, 2 atm. Between left and left for 200 hours, between wiring No insulation failure was observed.

[0358] 実施例 2— 2  [0358] Example 2-2

合成例:本発明の二トリル基含有重合性ポリマー Bの合成  Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer B of the present invention

ヒドロキシェチルアタリレート（市販品、東京化成製） 200mLを水 600mLに溶解し た。得られた水溶液に酢酸ェチル 400mLを加え、油層を分離した。次に、塩化ナトリ ゥム（和光純薬 (株)製） lOOgを水層に溶解させ、その後、酢酸ェチル 200mLを用い て 2回抽出を行った。その後、抽出物を無水硫酸マグネシウムで乾燥し、 p—メトキシ ノ、イドロキノンを 0. 04g添カロし、酢酸ェチルを適度に減圧留去させた。減圧留去後 に、 NMRで確認すると酢酸ェチルが 6. 5質量％残存していた。  200 mL of hydroxyethyl acrylate (commercially available, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 600 mL of water. To the obtained aqueous solution, 400 mL of ethyl acetate was added, and the oil layer was separated. Next, sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) lOOg was dissolved in the aqueous layer, and then extracted twice using 200 mL of ethyl acetate. Thereafter, the extract was dried over anhydrous magnesium sulfate, 0.04 g of p-methoxyno and idroquinone were added, and ethyl acetate was distilled off under reduced pressure. After distillation under reduced pressure, 6.5% by mass of ethyl acetate remained as confirmed by NMR.

また、ガスクロマトグラフィー（GC)にてヒドロキシェチルアタリレートの市販品中の 2 官能アタリレートの含有量を測定すると 0. 28質量％であったが、上記のように精製し たものを測定すると、 2官能アタリレートの含有量は検出限界以下であった。  In addition, when the content of difunctional acrylate was measured by gas chromatography (GC) in the commercially available product of hydroxyethyl acrylate, it was 0.28% by mass, but it was measured as purified above. Then, the content of the bifunctional acrylate was below the detection limit.

[0359] 500mLの 3つ口フラスコに N—メチルピロリドンを 20mL、上述の方法で精製された ヒドロキシェチノレアタリレート 2. 32g、シァノエチノレアタリレート 10. Olgを人れ、 75°C に昇温し、その中に、 V— 601 (前述）：0. 23g、及び N—メチルピロリドン 5mLの混 合液を 1時間かけて滴下した。滴下終了後 1時間後に、 80°Cに昇温し 1時間反応さ せた。  [0359] 20 mL of N-methylpyrrolidone in a 500 mL three-necked flask, 2.32 g of hydroxyethinorea tallylate purified by the above method, 10. The mixture was added dropwise over 1 hour with a mixture of V-601 (described above): 0.23 g and N-methylpyrrolidone 5 mL. One hour after the completion of the dropwise addition, the temperature was raised to 80 ° C. and reacted for 1 hour.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 29g、ジブチルチンジラ ゥレート 0. 29g、力レンズ AOI (商品名、昭和電工（株）製） 18. 56g、及び N—メチル ピロリドン 19gを加え、 55°C、 6時間反応を行った。その後、反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反応終了後、水で再沈を行い、固形物を取り 出し、本発明の二トリル基含有重合性ポリマー Bを 25g得た。  Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, power lens AOI (trade name, manufactured by Showa Denko KK) 18.56 g and N-methylpyrrolidone 19 g are added to the above reaction solution. The reaction was performed at ° C for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water to take out a solid, and 25 g of the nitrile group-containing polymerizable polymer B of the present invention was obtained.

[0360] 構造の同定 [0360] Structural identification

合成した二トリル基含有重合性ポリマー Bを重 DMSO (ジメチルスルホキシド）に溶 解させ、 300MHzの NMR (商品名： AV— 300、ブルカー製）にて測定を行った。二 トリル基含有ユニットに相当するピークが 4· 3-4. 05ppm (2H分）、 2· 9— 2· 8pp m (2H分）、 2. 5- 1. 3ppm (3H分）にブロードに観察され、重合性基含有ユニット に相当するピークが 7. 2- 7. 3ppm (lH分）、 6. 4— 6· 3ppm (lH分）、 6. 2— 6. lppm (lH分）、 6. 0- 5. 9ppm (lH分）、 4. 3— 4. 05ppm (6H分）、 3. 3— 3. 2p pm (2H分）、 2. 5- 1. 3ppm (3H分）にブロードに観察され、重合性基含有ユニット ：二トリル基含有ユニット = 20： 80 (mol比）であることが分かった。 The synthesized nitrile group-containing polymerizable polymer B was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). Peaks corresponding to di-tolyl group-containing units are broadly observed at 4.3-3.05 ppm (2H min), 2.9—2.8ppm (2H min), 2.5-1-1.3 ppm (3H min) The peaks corresponding to the polymerizable group-containing units are 7.2-7.3 ppm (lH), 6.4—6.3 ppm (lH), 6.2—6. lppm (lH component), 6.0-0.5.9 ppm (lH component), 4.3—4.05 ppm (6H component), 3.3—3.2 p pm (2H component), 2.5-1-1.3 ppm It was observed broadly at (3H), and it was found that the polymerizable group-containing unit: nitrile group-containing unit = 20: 80 (mol ratio).

[0361] 分子量の測定 [0361] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Bを THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 23. 75 分にピークが現れ、ポリスチレン換算で Mw= 22000 (Mw/Mn = 2· 1)であること が分かった。  The synthesized nitrile group-containing polymerizable polymer B was dissolved in THF, and the molecular weight was measured using a high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23.75 minutes and was found to be Mw = 22,000 (Mw / Mn = 2 · 1) in terms of polystyrene.

[0362] 二トリル基含有重合性ポリマー Bの使用態様  [0362] Usage of nitrile group-containing polymerizable polymer B

上記のようにして合成された二トリル基含有重合性ポリマー Bを用いた以外は、すべ て実施例 2— 1と同様にして組成物を調製し、これを用いて積層体を形成し、櫛形配 線 (金属パターン材料)を作製した。  A composition was prepared in the same manner as in Example 2-1, except that the nitrile group-containing polymerizable polymer B synthesized as described above was used, and this was used to form a laminate, which was then comb-shaped. Wiring (metal pattern material) was produced.

得られた櫛形配線について、実施例 2—1と同様にして実験したところ、配線間の 絶縁不良は見られなかった。  When the obtained comb-shaped wiring was tested in the same manner as in Example 2-1, no insulation failure was observed between the wirings.

[0363] 実施例 2— 3 [0363] Example 2-3

合成例:本発明の二トリル基含有重合性ポリマー Cの合成  Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer C of the present invention

500mLの 3つ口フラスコにエチレングリコールジアセテートを l lmL入れ、 75°Cに 昇温し、その中に、実施例 2— 2に記載の方法で精製されたヒドロキシェチルアタリレ 一卜 1. 39g、シァノエチルアタリレー卜 6. 00g、 V— 601 (前述）： 0. 1382g、及びェ チレングリコールジアセテート l lmLの混合液を 2. 5時間かけて滴下した。滴下終了 後、 80°Cに昇温し 3時間反応させた。  In a 500 mL three-necked flask, add 1 mL of ethylene glycol diacetate, raise the temperature to 75 ° C, and add hydroxyethyl ateryl purified by the method described in Example 2-2 1. A mixed solution of 39 g, cyanoethyl attareione 6.00 g, V-601 (previously described): 0.1382 g, and 1 mL of ethylene glycol diacetate was added dropwise over 2.5 hours. After completion of dropping, the temperature was raised to 80 ° C. and reacted for 3 hours.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 06g、ネオスタン U— 6 00 (前述） 0. 13g、力レンズ AOI (商品名、昭和電工（株）製） 3· 84g、エチレングリコ ールジアセテート（SP値： 20. 79MPa1/2) 3. 8gを加え、 55°C、 6時間反応を行ったIn the above reaction solution, ditertiary butyl hydroquinone 0.06 g, neostan U—600 (previously mentioned) 0.13 g, force lens AOI (trade name, manufactured by Showa Denko KK) 3.84 g, ethylene glycol diacetate (SP value) : 20. 79MPa 1/2 ) 3. 8g was added and reacted at 55 ° C for 6 hours.

〇 Yes

その後、反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反応終了 後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性ポリマー C を 3g得た。 [0364] 構造の同定 Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain 3 g of the nitrile group-containing polymerizable polymer C of the present invention. [0364] Structural identification

合成した二トリル基含有重合性ポリマー Cを重 DMSO (ジメチルスルホキシド）に溶 解させ、 300MHzの NMR (商品名： AV— 300、ブルカー製）にて測定を行った。二 トリル基含有ユニットに相当するピークが 4· 3-4. 05ppm (2H分）、 2· 9— 2· 8pp m (2H分）、 2. 5- 1. 3ppm (3H分）にブロードに観察され、重合性基含有ユニット に相当するピークが 7. 2- 7. 3ppm (lH分）、 6. 4— 6· 3ppm (lH分）、 6. 2— 6. lppm (lH分）、 6. 0- 5. 9ppm (lH分）、 4. 3— 4. 05ppm (6H分）、 3. 3— 3. 2p pm (2H分）、 2. 5- 1. 3ppm (3H分）にブロードに観察され、重合性基含有ユニット ：二トリル基含有ユニット = 21： 79 (mol比）であることが分かった。  The synthesized nitrile group-containing polymerizable polymer C was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). Peaks corresponding to di-tolyl group-containing units are broadly observed at 4.3-3.05 ppm (2H min), 2.9—2.8ppm (2H min), 2.5-1-1.3 ppm (3H min) The peaks corresponding to the polymerizable group-containing units are 7.2-7. 3 ppm (lH component), 6.4—6.3 ppm (lH component), 6.2— 6. lppm (lH component), 6. Broadly observed at 0-5.9 ppm (lH), 4. 3—4.05 ppm (6H), 3.3—3.2 p pm (2H), 2.5-1.3 ppm (3H) It was found that the polymerizable group-containing unit: nitrile group-containing unit = 21: 79 (mol ratio).

[0365] 分子量の測定 [0365] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Cを THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 23. 75 分にピークが現れ、ポリスチレン換算で Mw= 84000 (Mw/Mn = 2· 9)であること が分かった。  The synthesized nitrile group-containing polymerizable polymer C was dissolved in THF, and the molecular weight was measured using a high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23.75 minutes and was found to be Mw = 84000 (Mw / Mn = 2 · 9) in terms of polystyrene.

[0366] 二トリル基含有重合性ポリマー Cの使用態様  [0366] Usage of nitrile group-containing polymerizable polymer C

上記のようにして合成された二トリル基含有重合性ポリマー Cを用いた以外は、すべ て実施例 2— 1と同様にして組成物を調製し、これを用いて積層体を形成し、櫛形配 線 (金属パターン材料)を作製した。  A composition was prepared in the same manner as in Example 2-1, except that the nitrile group-containing polymerizable polymer C synthesized as described above was used. Wiring (metal pattern material) was produced.

得られた櫛形配線について、実施例 2—1と同様にして実験したところ、配線間の 絶縁不良は見られなかった。  When the obtained comb-shaped wiring was tested in the same manner as in Example 2-1, no insulation failure was observed between the wirings.

[0367] 実施例 2— 4 [0367] Example 2-4

合成例:本発明の二トリル基含有重合性ポリマー Dの合成  Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer D of the present invention

500mLの 3つ口フラスコにジエチレングリコールジアセテートを 30mL入れ、 75°C に昇温し、その中に、実施例 2— 2に記載の方法で精製されたヒドロキシェチルアタリ レー卜 3. 72g、シァノエチルアタリレー卜 16. 01g、 V— 601 (前述）： 0. 0737g、及び ジエチレングリコールジアセテート 30mLの混合液を 2. 5時間かけて滴下した。滴下 終了後、 80°Cに昇温し 3時間反応させた。  30 mL of diethylene glycol diacetate is placed in a 500 mL three-necked flask and heated to 75 ° C. In this, 3.72 g of hydroxyethyl talylate purified by the method described in Example 2-2 is added. Noethyl Atollerin® 16.01 g, V-601 (described above): 0.0737 g, and 30 mL of diethylene glycol diacetate were added dropwise over 2.5 hours. After completion of the dropwise addition, the temperature was raised to 80 ° C and reacted for 3 hours.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 16g、ネオスタン U— 6 00 (前述） 0. 32g、力レンズ AOI (商品名、昭和電工（株）製） 9· 6g、及びジエチレン グリコールジアセテート（SP値： 20· 75MPa1/2) 9. 6gを加え、 55。C、 6時間反応を 行った。その後、反応液にメタノールを 3. 6g加え、更に 1. 5時間反応を行った。反 応終了後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性ポリ マー Dを 18g得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.16g, neostan U-6 00 (previously described) 0.32 g, force lens AOI (trade name, manufactured by Showa Denko KK) 9 · 6 g, and diethylene glycol diacetate (SP value: 20 · 75 MPa 1/2 ) 9.6 g were added, and 55. C, reaction was performed for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 18 g of the nitrile group-containing polymerizable polymer D of the present invention was obtained.

[0368] 構造の同定 [0368] Structural identification

合成した二トリル基含有重合性ポリマー Dを実施例 2— 2と同様にして NMR測定を 行ったところ、重合性基含有ユニット：二トリル基含有ユニット = 23： 77 (mol比）であ ることが分かった。  The synthesized nitrile group-containing polymerizable polymer D was subjected to NMR measurement in the same manner as in Example 2-2. As a result, the polymerizable group-containing unit: nitrile group-containing unit = 23: 77 (mol ratio). I understood.

[0369] 分子量の測定 [0369] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Dを THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 23. 75 分にピークが現れ、ポリスチレン換算で Mw= 93000 (Mw/Mn = 3· 2)であること が分かった。  The synthesized nitrile group-containing polymerizable polymer D was dissolved in THF, and molecular weight was measured using a high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23.75 minutes and was found to be Mw = 93000 (Mw / Mn = 3 · 2) in terms of polystyrene.

[0370] 二トリル基含有重合性ポリマー Dの使用態様  [0370] Usage mode of nitrile group-containing polymerizable polymer D

上記のようにして合成された二トリル基含有重合性ポリマー Dを用いた以外は、す ベて実施例 2— 1と同様にして組成物を調製し、これを用いて積層体を形成し、櫛形 配線 (金属パターン材料)を作製した。  Except for using the nitrile group-containing polymerizable polymer D synthesized as described above, a composition was prepared in the same manner as in Example 2-1, and a laminate was formed using this. Comb wiring (metal pattern material) was prepared.

得られた櫛形配線について、実施例 2—1と同様にして実験したところ、配線間の 絶縁不良は見られなかった。  When the obtained comb-shaped wiring was tested in the same manner as in Example 2-1, no insulation failure was observed between the wirings.

[0371] 実施例 2— 5〜2— 13 [0371] Examples 2-5 to 2-13

実施例 2— 5〜2— 13として、以下に示す合成例にて、本発明の二トリル基含有重 合性ポリマー E〜Mを合成した。  As Examples 2-5 to 2-13, nitrile group-containing polymerizable polymers E to M of the present invention were synthesized in the following synthesis examples.

[0372] 合成例:本発明の二トリル基含有重合性ポリマー Eの合成 Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer E of the present invention

300mlの三口フラスコに、ジエチレングリコールジアセテート 29gを入れ、窒素気流 下、 75°Cまで加熱した。そこへ、実施例 2— 2と同様の手法により精製を行った 2—ヒ ドロキシェチノレアタリレート 3. 72g、 2—シァノエチノレアタリレート 16. Olg、及び V— 601 (前述） 0· 1842gのジエチレングリコーノレジアセテート 30g溶 ί夜を、 2· 5日寺 力、 けて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温ま で、反応溶液を冷却した。 In a 300 ml three-necked flask, 29 g of diethylene glycol diacetate was placed and heated to 75 ° C. under a nitrogen stream. Then, 2-Hydrochechinorea Talerate 3.72 g, 2-Cyanethinorea Talelate 16. Olg, and V-601 (described above) were purified by the same method as in Example 2-2. · 1842g diethylene glyconoresiacetate 30g melt night, 2 · 5 days temple power, Dripped. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 16g、ネオスタン U— 6 00 (前述） 0. 31gを加え、力レンズ MOI (商品名、昭和電工（株）製） 10. 28gを、ジ エチレングリコールジアセテート（SP値： 20. 75MPa1/2) 10. 28gに溶解させ反応 溶液に加え、 55°C、 6時間反応を行った。その後、反応液にメタノールを 2. 05g加え 、更に 1. 5時間反応を行った。反応終了後、水で再沈を行い、固形物を取り出し、本 発明の二トリル基含有重合性ポリマー Eを 18g得た。 Add 0.16 g ditertiary butylhydroquinone and 0.31 g neostan U-6 00 (described above) to the above reaction solution, and add 10.28 g power lens MOI (trade name, manufactured by Showa Denko KK) to diethylene glycol. Diacetate (SP value: 20. 75 MPa 1/2 ) 10. Dissolved in 28 g, added to the reaction solution, and reacted at 55 ° C for 6 hours. Thereafter, 2.05 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain 18 g of the nitrile group-containing polymerizable polymer E of the present invention.

[0373] 構造の同定 [0373] Structure identification

合成した二トリル基含有重合性ポリマー Eを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに 相当するピーク力 3-4. 0ppm (2H分）、 2. 9— 2. 75ppm (2H分）、 2. 5— 1. 3 ppm (3H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 4 - 7. Oppm (lH分）、 6. 1— 6. Oppm (lH分）、 5. 7— 5. 6ppm (lH分）、 4. 3— 4 . 0ppm (6H分）、 3. 4— 3. 2ppm (2H分）、 2. 5— 1. 3ppm (3H分）、 1. 9— 1. 8p pm (3H分）にブロードに観察され、重合性基含有ユニット:二トリル基含有ユニット = 22： 78 (mol比）であることが分かった。  The synthesized nitrile group-containing polymerizable polymer E was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing units 3-4. 0 ppm (2H min), 2. 9— 2. 75 ppm (2 H min), 2.5— 1. 3 ppm (3 H min) Peaks corresponding to the polymerizable group-containing units are 7.4-7. Oppm (lH content), 6.1—6 Oppm (lH content), 5.7—5.6 ppm (lH content), 4.3— 4.0 ppm (6H min), 3.4—3.2 ppm (2H min), 2.5—1.3 ppm (3H min), 1.9—1.8 p pm (3H min) It was found that the polymerizable group-containing unit: nitrile group-containing unit = 22: 78 (mol ratio).

[0374] 分子量の測定 [0374] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Eを、 THFに溶解させ、高速 GPC (商品名 ： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 20. 1 1分にピークが現れ、ポリスチレン換算で Mw= 78000 (Mw/Mn = 3· 11)であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer E was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 20. 11 minutes, and the component force was Mw = 78000 (Mw / Mn = 3 · 11) in terms of polystyrene.

[0375] 合成例:本発明の二トリル基含有重合性ポリマー Fの合成  [0375] Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer F of the present invention

1000mlの三口フラスコに、 N, N—ジメチルァセトアミド 35gを入れ、窒素気流下、 75°Cまで加熱した。そこへ、下記構造のモノマー 10· 25g、 2—シァノエチルアタリレ ート 24. 82g、及び V— 601 (前述） 0. 5710gの N, N—ジメチルァセトアミド 35g溶 液を、 2. 5時間かけて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した 。その後、室温まで、反応溶液を冷却した。 上記の反応溶液に、氷冷下、 4—ヒドロキシテンポ 0. 427g、トリェチルァミン 12. 5 4g、及び N, N—ジメチノレアセトアミド 315· 6gをカロ免、室温、 4日寺間反応を fiつた。 反応終了後、イソプロピルアルコール：へキサン = 1 : 3で再沈を行い、固形物を取り 出し、本発明の二トリル基含有重合性ポリマー Fを 24g得た。 In a 1000 ml three-necked flask, 35 g of N, N-dimethylacetamide was placed and heated to 75 ° C. under a nitrogen stream. Thereto, 10.25 g of monomer having the following structure, 24.82 g of 2-cyanoethyl acrylate and V-601 (as described above) 0.5710 g of N, N-dimethylacetamide 35 g of solution 2. It was added dropwise over 5 hours. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature. To the above reaction solution, 4-hydroxytempo (0.427 g), triethylamine (12.5 4 g), and N, N-dimethylenoacetamide (315 · 6 g) were subjected to a calorie-free reaction at room temperature for 4 days under ice-cooling. After completion of the reaction, reprecipitation was performed with isopropyl alcohol: hexane = 1: 3, and the solid matter was taken out to obtain 24 g of the nitrile group-containing polymerizable polymer F of the present invention.

[0376] [化 36]  [0376] [Chemical 36]

Figure imgf000111_0001
Figure imgf000111_0001

[0377] 構造の同定 [0377] Structural identification

合成した二トリル基含有重合性ポリマー Fを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに 相当するピーク力 3-4. 05ppm (2H分）、 2. 9— 2. 8ppm (2H分）、 2. 5— 1. 3 ppm (3H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 2 - 7. 3ppm (lH分）、 6. 4— 6. 3ppm (lH分）、 6. 2— 6. lppm (lH分）、 6. 0— 5 • 9ppm (lH分）、 4· 4-4. 05ppm (4H分）、 2· 5- 1. 3ppm (3H分） ίこフ、、ロード、 ίこ 観察され、重合性基含有ユニット：二トリル基含有ユニット = 23： 77 (mol比）であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer F was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing unit 3-4. 05ppm (2H min), 2.9—2.8 ppm (2H min), 2.5—1.3 ppm (3H min) Peaks corresponding to polymerizable group-containing units are 7.2-7. 3 ppm (lH component), 6.4— 6. 3 ppm (lH component), 6.2 — 6. lppm (lH component), 6.0 — 5 • 9ppm (for 1H), 4 · 4-4. 05ppm (for 4H), 2 · 5–1. 3ppm (for 3H) The trityl group-containing unit is 23:77 (mol ratio).

[0378] 分子量の測定  [0378] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Fを、 THFに溶解させ、高速 GPC (商品名 ： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 22. 4 7分にピークが現れ、ポリスチレン換算で Mw= 12000 (Mw/Mn= l . 78)であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer F was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 22.47 minutes, and the component force was Mw = 12000 (Mw / Mn = l.78) in terms of polystyrene.

[0379] 合成例:本発明の二トリル基含有重合性ポリマー Gの合成  Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer G of the present invention

500mlの三口フラスコに、 N, N—ジメチルァセトアミド 40gを入れ、窒素気流下、 7 5。Cまでカロ熱した。そこへ、 クリノレ酸 5. 04g、 2—シ ノエチノレ クリレー卜 35. 03g 、及び V— 601 (前述） 0. 8059gの N, N—ジメチノレアセトアミド 40g溶 ί夜を、 2. 5日寺 間かけて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室 温まで、反応溶液を冷却した。 In a 500 ml three-necked flask, put 40 g of N, N-dimethylacetamide under nitrogen flow. Heated up to C. There, clinoleic acid 5.04g, 2-sino-Ethinocrera 卜 35.03g, and V-601 (as described above) 0.859g N, N-Dimethyloleacetamide 40g melted night, 2.5 days temple And dripped. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Then room The reaction solution was cooled to warm.

上記の反応溶液に、室温下、ジターシャリーブチルハイドロキノン 0. 04g、トリェチ ルベンジルアンモニゥムクロライド 3· 19g、サイクロマー A (前述） 25· 52gをカロえ、 10 0°C、 5時間反応を行った。反応終了後、酢酸ェチル：へキサン = 2 : 3で再沈を行い 、固形物を取り出し、本発明の二トリル基含有重合性ポリマー Gを 30g得た。  Carry out 0.04 g ditertiary butylhydroquinone, 3 · 19 g triethylbenzylammonium chloride and 25 · 52 g cyclomer A (described above) at room temperature at room temperature for 5 hours at room temperature. went. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane = 2: 3, and the solid matter was taken out to obtain 30 g of the nitrile group-containing polymerizable polymer G of the present invention.

[0380] 構造の同定  [0380] Structural identification

合成した二トリル基含有重合性ポリマー Gを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに 相当するピーク力 4— 4. 2ppm (2H分）、 3. 0— 2. 8ppm (2H分）、 2. 6— 1. 3p pm (3H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 6 - 7. 5ppm (lH分）、 6. 5— 6. 3ppm (lH分）、 6. 3— 6. lppm (lH分）、 6. 0— 5 . 8ppm (lH分）、 4. 9— 4. 7 (1H分）、 4. 2— 4. 0 (2H分）、 4. 0— 3. 7 (1H分）、 2 . 7- 1. 3ppm (10H分）にブロードに観察され、重合性基含有ユニット：二トリル基含 有ユニット = 35： 65 (mol比）であることが分かった。  The synthesized nitrile group-containing polymerizable polymer G was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing unit 4—4.2 ppm (2H min), 3.0—2.8 ppm (2H min), 2.6—1.3 p pm (3H min) Peaks corresponding to the polymerizable group-containing units are 7.6-7.5 ppm (lH component), 6.5—6.3 ppm (lH component), 6.3— 6. lppm (lH component), 6.0— 5.8ppm (1H), 4. 9—4.7 (1H), 4.2—4.0 (2H), 4.0—3.7 (1H), 2.7-1. It was observed broadly at 3 ppm (10H), and it was found that the polymerizable group-containing unit: nitrile group-containing unit = 35: 65 (mol ratio).

[0381] 分子量の測定  [0381] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Gを、 THFに溶解させ、高速 GPC (商品名 ： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 22. 2 3分にピークが現れ、ポリスチレン換算で Mw= 23000 (Mw/Mn = 2· 17)であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer G was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 22.23 minutes, and the component force was Mw = 23,000 (Mw / Mn = 2 · 17) in terms of polystyrene.

[0382] 合成例:本発明の二トリル基含有重合性ポリマー Hの合成  [0382] Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer H of the present invention

300mlの三口フラスコに、ジエチレングリコールジアセテート 21gを入れ、窒素気流 下、 75°Cまで加熱した。そこへ、実施例 2— 2と同様の手法により精製を行った 2—ヒ ドロキシュチノレ タリレート 2· 69g、 p—シ ノベンジノレ タリレート 17· 37g、及び V — 601 (前述） 0· 0534gのジエチレングリコールジアセテート 20g溶液を、 2· 5時間 力、けて滴下した。滴下終了後、 2時間攪拌した後 80°Cまで加熱し、更に 2時間撹拌し た。その後、室温まで、反応溶液を冷却した。  In a 300 ml three-necked flask, 21 g of diethylene glycol diacetate was placed and heated to 75 ° C. under a nitrogen stream. Then, 2-Hydroxinore Talelate 2.69 g, p-Sinobenzinore Talerate 17 · 37 g, and V — 601 (previously described) 0 · 0534 g of diethylene glycol diacetate 20 g were purified by the same method as in Example 2-2. The solution was dripped in force for 2.5 hours. After completion of dropping, the mixture was stirred for 2 hours, heated to 80 ° C, and further stirred for 2 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 12g、ネオスタン U— 6 00 (前述） 0. 23g、力レンズ AOI (商品名、昭和電工（株）製） 7· 09g、及びジェチレ ングリコールジァセテート（SP値： 20. 75MPa1/2) 27. 09gをカロえ、 55。C、 6時間反 応を行った。その後、反応液にメタノールを 1. 48g加え、更に 1. 5時間反応を行った 。反応終了後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性 ポリマー Hを 21 g得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.12 g, neostan U—600 (previously described) 0.23 g, force lens AOI (trade name, manufactured by Showa Denko KK) 7.09 g, and jetile Glycol dicetate (SP value: 20. 75 MPa 1/2 ) 27. C, reacted for 6 hours. Thereafter, 1.48 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, the solid was taken out, and 21 g of the nitrile group-containing polymerizable polymer H of the present invention was obtained.

[0383] 構造の同定  [0383] Structural identification

合成した二トリル基含有重合性ポリマー Hを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに 相当するピーク力 8 - 7. 65ppm (2H分）、 7. 5— 7. 3ppm (2H分）、 5. 2— 4. 9 ppm (2H分）、 2· 5- 1. 3ppm (3H分）にブロードに観察され、重合性基含有ュニッ 卜に申目当するピーク力 7. 4- 7. Oppm (lH分）、 6. 4- 6. 2ppm(lH分）、 6. 2- 6 . Oppm (lH分）、 6. 0- 5. 8ppm (lH分）、 4. 2— 3. 9ppm (6H分）、 3. 4— 3. 2p pm (2H分）、 2. 5- 1. 3ppm (3H分）にブロードに観察され、重合性基含有ユニット ：二トリル基含有ユニット = 23： 77 (mol比）であることが分かった。  The synthesized nitrile group-containing polymerizable polymer H was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing unit 8-7. 65 ppm (2H min), 7.5—7.3 ppm (2H min), 5.2—4.99 ppm (2H min), 2.5-1 Peak force observed broadly at 3ppm (3H min) and corresponding to the polymerizable group-containing unit 7.4- 7. Oppm (lH min), 6. 4-6.2 2ppm (lH min), 6 2- 6. Oppm (lH component), 6.0-5.8 ppm (lH component), 4.2—3.9 ppm (6H component), 3.4—3.2 p pm (2H component), 2. 5- 1. Broadly observed at 3ppm (3H), it was found that the polymerizable group-containing unit: nitrile group-containing unit = 23:77 (mol ratio).

[0384] 分子量の測定  [0384] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Hを、 THFに溶解させ、高速 GPC (商品名 ： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 19. 8 5分にピークが現れ、ポリスチレン換算で Mw= 149000 (Mw/Mn = 4. 46)である ことが分力、つた。  The synthesized nitrile group-containing polymerizable polymer H was dissolved in THF, and the molecular weight was measured using a high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 19.85 minutes, and it was found that Mw = 149000 (Mw / Mn = 4.46) in terms of polystyrene.

[0385] 合成例:本発明の二トリル基含有重合性ポリマー Iの合成  [0385] Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer I of the present invention

300mlの三口フラスコに、ジエチレングリコールジアセテート 20gを入れ、窒素気流 下、 75°Cまで加熱した。そこへ、実施例 2— 2と同様の手法により精製を行った 2—ヒ ドロキシェチノレメタタリレート 3. 77g、 2—シァノエチノレメタタリレート 16. 15g、及び V — 601 (前述） 0· 0668gのジエチレングリコールジアセテート 20g溶液を、 2· 5時間 力、けて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温 まで、反応溶液を冷却した。  In a 300 ml three-necked flask, 20 g of diethylene glycol diacetate was placed and heated to 75 ° C. under a nitrogen stream. To this, 2-hydrochichechinole metathalylate 3.77 g purified by the same method as in Example 2-2, 2-cyanethinoremethalate 16.15 g, and V—601 (described above) 0 · A solution of 0668 g of 20 g of diethylene glycol diacetate was added dropwise for 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 15g、ネオスタン U— 6 00 (前述） 0. 29g、力レンズ AOI (商品名、昭和電工（株）製） 8· 82g、及びジェチレ ングリコールジァセテート（SP値： 20. 75MPa1/2) 27. 82gをカロえ、 55。C、 6時間反 応を行った。その後、反応液にメタノールを 1. 86g加え、更に 1. 5時間反応を行った 。反応終了後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性 ポリマー Iを 10g得た。 In the above reaction solution, 0.15 g ditertiary butyl hydroquinone, 0.29 g Neostan U—600 (previously described), 0.28 g power lens AOI (trade name, manufactured by Showa Denko KK), and 82 g Setate (SP value: 20. 75 MPa 1/2 ) 27. C, 6 hours anti I did it. Thereafter, 1.86 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, the solid was taken out, and 10 g of the nitrile group-containing polymerizable polymer I of the present invention was obtained.

[0386] 構造の同定 [0386] Structural identification

合成した二トリル基含有重合性ポリマー Iを重 DMSOに溶解させ、 300MHzの NM R (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに相 当するピーク力 25-4. 0ppm (2H分）、 2. 95— 2. 8ppm (2H分）、 2. 1— 0. 5p pm (5H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 4 - 7. 0ppm (lH分）、 6. 5— 6. 3ppm (lH分）、 6. 3— 6. 0ppm (lH分）、 6. 0— 5 . 8ppm (lH分）、 4. 2— 3. 9ppm (6H分）、 3. 5— 3. 3ppm (2H分）、 2. 1— 0. 5p pm (5H分）にブロードに観察され、重合性基含有ユニット:二トリル基含有ユニット = 24： 76 (mol比）であることが分かった。  The synthesized nitrile group-containing polymerizable polymer I was dissolved in heavy DMSO and measured with 300 MHz NM R (trade name: AV-300, manufactured by Bruker). Peak forces corresponding to nitrile group-containing units 25-4. 0ppm (2H min), 2.95—2.8 ppm (2H min), 2.1—0.5ppm (5H min) broadly observed The peaks corresponding to the polymerizable group-containing units are 7.4-7.0 ppm (lH component), 6.5—6.3 ppm (lH component), 6.3—6.0 ppm (lH component), 6.0 — 5.8ppm (lH min), 4.2—3.9 ppm (6H min), 3.5—3.3 ppm (2H min), 2.1—0.5 p pm (5H min) It was found that the polymerizable group-containing unit: nitrile group-containing unit = 24: 76 (mol ratio).

[0387] 分子量の測定 [0387] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Iを、 THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 18. 52 分にピークが現れ、ポリスチレン換算で Mw= 238000 (Mw/Mn = 2· 56)であるこ とが分かった。  The synthesized nitrile group-containing polymerizable polymer I was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 18.52 minutes and was found to be Mw = 238000 (Mw / Mn = 2 · 56) in terms of polystyrene.

[0388] 合成例:本発明の二トリル基含有重合性ポリマー Jの合成  Synthesis Example: Synthesis of the nitrile group-containing polymerizable polymer J of the present invention

300mlの三口フラスコに、ジエチレングリコールジアセテート 33gを入れ、窒素気流 下、 75°Cまで加熱した。そこへ、実施例 2— 2と同様の手法により精製を行った 2—ヒ ドロキシェチノレメタタリレート 4. 16g、 2—シァノエチノレメタタリレート 17. 80g、及び V — 601 (前述） 0· 1842gのジエチレングリコールジアセテート 33g溶液を、 2· 5時間 力、けて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温 まで、反応溶液を冷却した。  In a 300 ml three-necked flask, 33 g of diethylene glycol diacetate was placed and heated to 75 ° C. under a nitrogen stream. To this, 2-hydroxychetinoremetatalylate 4.16 g, 2-cyanethinoremetatalate 17.80 g, and V—601 (described above) were purified in the same manner as in Example 2-2. · 1842 g of a solution of 33 g of diethylene glycol diacetate was added dropwise for 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 16g、ネオスタン U— 6 00 (前述） 0. 32g、力レンズ MOI (商品名、昭和電工（株）製） 10· 66g、及びジェチ レングリコールジアセテート（SP値： 20· 75MPa1/2) 10. 66gを加え、 55。C、 6時間 反応を行った。その後、反応液にメタノールを 2. 05g加え、更に 1. 5時間反応を行 つた。反応終了後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重 合性ポリマー Jを 20g得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.16 g, neostan U-6 00 (previously described) 0.32 g, force lens MOI (trade name, manufactured by Showa Denko KK) 10.66 g, and ethylene glycol diacetate (SP value: 20 · 75 MPa 1/2 ) 10. Add 66 g and 55. C, reaction was performed for 6 hours. Then, 2.05 g of methanol was added to the reaction solution, and the reaction was further continued for 1.5 hours. I got it. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 20 g of the nitrile group-containing polymeric polymer J of the present invention was obtained.

[0389] 構造の同定 [0389] Structural identification

合成した二トリル基含有重合性ポリマー Jを重 DMSOに溶解させ、 300MHzの NM R (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに相 当するピーク力 2- 3. 95ppm (2H分）、 2. 9— 2. 75ppm (2H分）、 2. 1— 0. 6p pm (5H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 4 - 7. Oppm (lH分）、 6. 1— 6. Oppm (lH分）、 5. 7— 5. 6ppm (lH分）、 4. 2— 3 • 95ppm (6H分）、 3. 35— 3· 2ppm (2H分）、 2. 1— 0· 6ppm (8H分）にブロード、 に観察され、重合性基含有ユニット：二トリル基含有ユニット = 24 : 76 (mol比）である ことが分力、つた。  The synthesized nitrile group-containing polymerizable polymer J was dissolved in heavy DMSO and measured with 300 MHz NM R (trade name: AV-300, manufactured by Bruker). Peak force equivalent to nitrile group-containing units 2-3. 95 ppm (2H min), 2. 9— 2. 75 ppm (2 H min), 2.1 — 0.6 p pm (5 H min) , Peaks corresponding to polymerizable group-containing units are 7.4-7. Oppm (lH component), 6.1 — 6. Oppm (lH component), 5.7—5.6 ppm (lH component), 4.2 — 3 • 95ppm (6H min.), 3. 35— 3 · 2ppm (2H min.), 2.1 — 0 · 6ppm (8H min.) Broad, observed in, polymerizable group-containing unit: nitrile group-containing unit = 24: 76 (mol ratio), the component force.

[0390] 分子量の測定 [0390] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Jを、 THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 19. 90 分にピークが現れ、ポリスチレン換算で Mw= 90000 (Mw/Mn = 2· 45)であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer J was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 19.90 minutes, and the component force was Mw = 90000 (Mw / Mn = 2 · 45) in terms of polystyrene.

[0391] 合成例:本発明の二トリル基含有重合性ポリマー Kの合成  [0391] Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer K of the present invention

300mlの三口フラスコに、 N—メチルー 2—ピロリドン 5gを入れ、窒素気流下、 75°C まで加熱した。そこへ、実施例 2— 2と同様の手法により精製を行った 2—ヒドロキシェ チノレアタリレート 0. 53g、 2, 2—ジェチノレー 4ーシァノーェチノレアタリレート 3. 85g、 V— 601 (前述） 0· 0530gの Ν—メチノレー 2—ピロリドン 4g溶 ί夜を、 2· 5日寺間力、けて 滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温まで、 反応溶液を冷却した。  A 300 ml three-necked flask was charged with 5 g of N-methyl-2-pyrrolidone and heated to 75 ° C. under a nitrogen stream. Thereto, 2-hydroxyethylenotale talirate purified by the same method as in Example 2-2 0.53 g, 2,2-jetinoreole 4-cyanose notalearelate 3.85 g, V-601 (Previously described) 0 · 0530 g of Ν-methinole 2-pyrrolidone 4 g was added dropwise for 2-5 days. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 02g、ネオスタン U— 6 00 (前述） 0. 05g、力レンズ AOI (商品名、昭和電工（株）製） 1 · 53g、及び N—メチ ルー 2—ピロリドン（SP値： 22. 94MPa1/2) l . 53gをカロえ、 55。C、 6時間反応を行つ た。その後、反応液にメタノールを 0. 29g加え、更に 1. 5時間反応を行った。反応終 了後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性ポリマー Kを lg得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.02 g, neostan U—600 (previously described) 0.05 g, force lens AOI (trade name, manufactured by Showa Denko KK) 1 · 53 g, and N—methyl 2 —Pyrrolidone (SP value: 22.94 MPa 1/2 ) l. C, reacted for 6 hours. Thereafter, 0.29 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation is performed with water, and the solid matter is taken out. I got K lg.

[0392] 構造の同定  [0392] Structural identification

合成した二トリル基含有重合性ポリマー Kを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。二トリル基含有ユニットに 相当するピーク力 9- 3. 65ppm (2H分）、 2. 5— 2. 3ppm (2H分）、 1. 7— 1. 4 ppm (2H分）、 1. 4- 1. lppm (4H分）、 0. 9— 0. 6ppm(6H分）、 2. 5— 1. 3ppm (3H分）にブロードに観察され、重合性基含有ユニットに相当するピークが 7. 4- 7. Oppm (lH分）、 6. 4- 6. 3ppm (lH分）、 6. 3— 6. lppm(lH分）、 6. 0— 5. 9 (1 H分）、 4. 2-4. 0ppm(6H分）、 3. 4— 3. 2ppm(2H分）、 2. 0— 1. 3ppm (3H分 )にブロードに観察され、重合性基含有ユニット：二トリル基含有ユニット = 25： 75 (m ol比）であることが分力、つた。  The synthesized nitrile group-containing polymerizable polymer K was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Peak force equivalent to a nitrile group-containing unit 9- 3.65 ppm (2H min), 2.5—2.3 ppm (2H min), 1.7—1.4 ppm (2H min), 1.4-1 lppm (4H min), 0.9—0.6 ppm (6H min), 2.5—1.3 3ppm (3H min) broadly observed, peaks corresponding to polymerizable group-containing units 7. Oppm (for 1H), 6. 4- 6. 3ppm (for 1H), 6.3— 6. lppm (for 1H), 6.0—5.9 (1 for H), 4.2-4 0 ppm (6H min), 3.4—3.2 ppm (2H min), 2.0—1.3 ppm (3H min), broadly observed, polymerizable group-containing unit: nitrile group-containing unit = 25: The component force was 75 (mol ratio).

[0393] 分子量の測定  [0393] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Kを、 THFに溶解させ、高速 GPC (商品名 ： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 23. 0 7分にピークが現れ、ポリスチレン換算で Mw= 6900 (Mw/Mn= l . 45)であるこ とが分力、つた。  The synthesized nitrile group-containing polymerizable polymer K was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 23.07 minutes, and the component force was Mw = 6900 (Mw / Mn = 1.45) in terms of polystyrene.

[0394] 合成例:本発明の二トリル基含有重合性ポリマー Lの合成  [0394] Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer L of the present invention

300mlの三口フラスコに、 N—メチルー 2—ピロリドン 25gを入れ、窒素気流下、 75 °Cまで加熱した。そこへ、実施例 2— 2と同様の手法により精製を行った 2—ヒドロキシ ュチノレ クリレート 3. 17g、 2—シ ノュチノレ クリレート 15. 37g、 クリ π二トリノレ 6. 52g、 V— 601 (前述） 0. 6286gの N—メチノレ一 2—ピロリドン 25g溶 ί夜を、 2. 5日寺 力、けて滴下した。滴下終了後、 80°Cまで加熱し、更に 3時間撹拌した。その後、室温 まで、反応溶液を冷却した。  A 300 ml three-necked flask was charged with 25 g of N-methyl-2-pyrrolidone and heated to 75 ° C. under a nitrogen stream. Then, 2-hydroxy turinole acrylate 3.17g, 2-cinutino acrylate 15.37g, chestnut π nitrinole 6.52g, V- 601 (previously described) 0 6286 g of N-methinole 2-pyrrolidone 25 g was melted and dropped for 2. days. After completion of dropping, the mixture was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0. 14g、ネオスタン U— 6 00 (前述） 0. 28g、力レンズ AOI (商品名、昭和電工（株）製） 8· 54g、及び N—メチ ルー 2—ピロリドン（SP値： 22· 94MPa1/2) 8. 54gを加え、 55。C、 6時間反応を行つ た。その後、反応液にメタノールを 1. 75g加え、更に 1. 5時間反応を行った。反応終 了後、水で再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性ポリマー Lを 18g得た。 In the above reaction solution, ditertiary butyl hydroquinone 0.14 g, neostan U-6 00 (previously described) 0.28 g, force lens AOI (trade name, manufactured by Showa Denko KK) 8 · 54 g, and N-methyl 2 - pyrrolidone (SP value: 22 · 94MPa 1/2) 8. 54g was added, 55. C, reacted for 6 hours. Thereafter, 1.75 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation is performed with water, and the solid matter is taken out. 18 g of L was obtained.

[0395] 構造の同定 [0395] Structural identification

合成した二トリル基含有重合性ポリマー Lを重 DMSOに溶解させ、 300MHzの N MR (商品名： AV— 300、ブルカー製）にて測定を行った。シァノエチルアタリレート ュュッ卜に申目当するピーク力 4.3-4.0ppm(2H分）、 3.0— 2.8ppm(2H分）、 2. 7-1.4ppm(3H分）にブロードに観察され、アクリロニトリルユニットに相当するピー クが 2.7-1.4ppm(3H分）にブロードに観察され、重合性基含有ユニットに相当す るピーク力 S7.4— 7.0ppm(lH分）、 6.4— 6.3ppm(lH分）、 6.3— 6. lppm(l H分）、 6.0-5.9(1H分）、 4.2— 4.0ppm(6H分）、 3.3— 3.2ppm(2H分）、 2 .7-1.4ppm(3H分）にブロードに観察され、重合性基含有ユニット：シァノエチル アタリレートユニット：アタリロニトリノレユニット = 12： 47 :41 (mol比）であることが分かつ た。  The synthesized nitrile group-containing polymerizable polymer L was dissolved in heavy DMSO and measured with 300 MHz N MR (trade name: AV-300, manufactured by Bruker). Acrylonitrile units are observed broadly at peak forces of 4.3-4.0ppm (2H min), 3.0-2.8ppm (2H min), and 2.7-1.4ppm (3H min) corresponding to Cyanethyl Atylate Ju A peak equivalent to 2.7-1.4 ppm (3H min) was observed broadly, and peak forces corresponding to polymerizable group-containing units S7.4—7.0 ppm (lH min), 6.4—6.3 ppm (lH min) , 6.3-6. lppm (l H min), 6.0-5.9 (1 H min), 4.2-4.0 ppm (6 H min), 3.3-3.2 ppm (2 H min), 2.7-1.4 ppm (3 H min) As a result, it was found that the polymerizable group-containing unit: cyanoethyl acrylated unit: alitronitrinole unit = 12: 47:41 (mol ratio).

[0396] 分子量の測定  [0396] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Lを、 THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 24.18 分にピークが現れ、ポリスチレン換算で Mw=4700(Mw/Mn=l.69)であること が分かった。  The synthesized nitrile group-containing polymerizable polymer L was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 24.18 minutes and was found to be Mw = 4700 (Mw / Mn = l.69) in terms of polystyrene.

[0397] 合成例：本発明の二トリル基含有重合性ポリマー Mの合成  [0397] Synthesis Example: Synthesis of nitrile group-containing polymerizable polymer M of the present invention

500mLの 3つ口フラスコにジメチルカーボネートを 10mL入れ、 65°Cに昇温し、そ の中に、実施例 2— 2に記載の方法で精製されたヒドロキシェチルアタリレート 3· 72g 、シァノエチノレアタリレート 16· 01g、V— 65:0.3974g、及びジメチルカーボネート 10mLの混合液を 2.5時間かけて滴下した。滴下終了後、ジメチルカーボネートを 2 5mL加え、さらに 65°Cで 3時間反応させた。反応終了後、ジメチルカーボネートを 14 mL足した。  10 mL of dimethyl carbonate was placed in a 500 mL three-necked flask and the temperature was raised to 65 ° C. In this, 3-72 g of hydroxyethyl talylate purified by the method described in Example 2-2, A mixture of ethinoreatalylate 16.01 g, V-65: 0.3974 g, and dimethyl carbonate 10 mL was added dropwise over 2.5 hours. After completion of the dropwise addition, 25 mL of dimethyl carbonate was added and further reacted at 65 ° C for 3 hours. After completion of the reaction, 14 mL of dimethyl carbonate was added.

上記の反応溶液に、ジターシャリーブチルハイドロキノン 0.15g、ネオスタン U— 6 00(前述） 0.38g、力レンズ AOI (商品名、昭和電工（株）製） 11· 6g、ジメチルカ一 ボネート（SP値： 22· 9MPa1/2)ll.6gを加え、 55°C、 6時間反応を行った。その後 、反応液にメタノールを 1.9g加え、更に 1.5時間反応を行った。反応終了後、水で 再沈を行い、固形物を取り出し、本発明の二トリル基含有重合性ポリマー Mを 12g得 た。 In the above reaction solution, ditertiary butyl hydroquinone 0.15 g, neostan U—600 (previously described) 0.38 g, force lens AOI (trade name, manufactured by Showa Denko KK) 11 · 6 g, dimethyl carbonate (SP value: 22) · 9MPa 1/2 ) ll.6g was added and reacted at 55 ° C for 6 hours. Thereafter, 1.9 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, with water Reprecipitation was performed, and the solid matter was taken out to obtain 12 g of the nitrile group-containing polymerizable polymer M of the present invention.

[0398] 構造の同定  [0398] Structural identification

合成した二トリル基含有重合性ポリマー Mを重 DMSO (ジメチルスルホキシド）に溶 解させ、 300MHzの NMR (商品名： AV— 300、ブルカー製）にて測定を行った。二 トリル基含有ユニットに相当するピークが 4· 3-4.05ppm(2H分）、 2· 9— 2· 8pp m(2H分）、 2.5-1.3ppm(3H分）にブロードに観察され、重合性基含有ユニット に相当するピークが 7.2-7.3ppm(lH分）、 6.4— 6· 3ppm(lH分）、 6.2— 6. lppm(lH分）、 6.0-5.9ppm(lH分）、 4.3— 4.05ppm(6H分）、 3.3— 3.2p pm(2H分）、 2.5-1.3ppm(3H分）にブロードに観察され、重合性基含有ユニット ：二トリル基含有ユニット = 25： 75 (mol比）である事が分かった。  The synthesized nitrile group-containing polymerizable polymer M was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured by 300 MHz NMR (trade name: AV-300, manufactured by Bruker). Peaks corresponding to ditolyl group-containing units are broadly observed at 4.3-4.05ppm (2H min), 2.9-2.8ppm (2H min), 2.5-1.3ppm (3H min), and polymerizability Peaks corresponding to group-containing units are 7.2-7.3ppm (lH content), 6.4—6.3ppm (lH content), 6.2—6 lppm (lH content), 6.0-5.9ppm (lH content), 4.3—4.05ppm (6H min), 3.3—3.2ppm (2H min), 2.5-1.3ppm (3H min) broadly observed, polymerizable group-containing unit: nitrile group-containing unit = 25: 75 (mol ratio) I understood that.

[0399] 分子量の測定 [0399] Measurement of molecular weight

合成した二トリル基含有重合性ポリマー Mを THFに溶解させ、高速 GPC (商品名： HLC— 8220GPC、東ソー製）を用いて分子量の測定を行った。その結果、 20.40 分にピークが現れ、ポリスチレン換算で Mw= 83000 (Mw/Mn = 2· 6)であること が分かった。  The synthesized nitrile group-containing polymerizable polymer M was dissolved in THF, and the molecular weight was measured using high-speed GPC (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). As a result, a peak appeared at 20.40 minutes and was found to be Mw = 83000 (Mw / Mn = 2 · 6) in terms of polystyrene.

Claims

請求の範囲 The scope of the claims [1] (al)基板上に、めっき触媒又はその前駆体と相互作用を形成する官能基を有し、 且つ、該基板と直接化学結合したポリマーからなるポリマー層を形成する工程； (a2)該ポリマー層にめっき触媒又はその前駆体を付与する工程;及び  [1] (al) A step of forming a polymer layer comprising a polymer having a functional group capable of interacting with a plating catalyst or a precursor thereof on the substrate and directly chemically bonded to the substrate; (a2) Applying a plating catalyst or a precursor thereof to the polymer layer; and (a3)該めっき触媒又はその前駆体に対してめつきを行う工程；  (a3) a step of performing plating on the plating catalyst or a precursor thereof; を含むこと、及び、前記ポリマー層が下記条件（1)〜（4)の全てを満たすことを特徴と する表面金属膜材料の作製方法：  And a method for producing a surface metal film material, wherein the polymer layer satisfies all of the following conditions (1) to (4): (1) 25°C— 50%相対湿度環境下における飽和吸水率が 0. 01〜； 10質量％； (1) Saturated water absorption at 25 ° C-50% relative humidity is 0.01 ~; 10% by mass; (2) 25°C— 95%相対湿度環境下における飽和吸水率が 0. 05〜20質量％;(2) Saturated water absorption at 25 ° C—95% relative humidity is 0.05 to 20% by mass; (3) 100°C煮沸水に 1時間浸漬した後の吸水率が 0. ；!〜 30質量％； (3) The water absorption after immersion for 1 hour in 100 ° C boiling water is 0; (4) 25°C— 50%相対湿度環境下において、蒸留水 5 しを滴下し、 15秒静置後 の表面接触角が 50〜； 150度。  (4) 25 ° C-In a 50% relative humidity environment, 5 drops of distilled water was dropped and the surface contact angle after standing for 15 seconds was 50 to 150 degrees. [2] 前記ポリマー層が下記条件（1 ' )〜（4' )の全てを満たすことを特徴とする請求項 1 に記載の表面金属膜材料の作製方法。  [2] The method for producing a surface metal film material according to [1], wherein the polymer layer satisfies all of the following conditions (1 ′) to (4 ′). (l ' ) 25°C— 50%相対湿度環境下における飽和吸水率が 0. 0；!〜 5質量％  (l ') 25 ° C—50% saturated water absorption under relative humidity is 0.0; (2 ' ) 25°C— 95 %相対湿度環境下における飽和吸水率が 0. 05〜； 10質量％  (2 ') 25 ° C—95% Saturated water absorption in relative humidity environment 0.05-; 10% by mass (3' ) 100°C煮沸水に 1時間浸漬した後の吸水率が 0. ；!〜 20質量％  (3 ') Water absorption after immersion in boiling water at 100 ° C for 1 hour is 0; (4' ) 25°C— 50%相対湿度環境下において、蒸留水 5 しを滴下し、 15秒静置後 の表面接触角が 55〜； 150度。  (4 ') 25 ° C-In a 50% relative humidity environment, 5 ml of distilled water was added dropwise, and the surface contact angle after standing for 15 seconds was 55 to 150 ° C. [3] 前記（al)工程が、基板上に、めっき触媒又はその前駆体と相互作用を形成する官 能基、及び重合性基を有するポリマーを直接化学結合させる工程を含むことを特徴 とする請求項 1又は請求項 2に記載の表面金属膜材料の作製方法。 [3] The step (al) includes a step of directly chemically bonding a functional group capable of forming an interaction with a plating catalyst or a precursor thereof and a polymer having a polymerizable group on a substrate. A method for producing a surface metal film material according to claim 1. [4] 前記 (al)工程が、（al— 1)基材上に、重合開始剤を含有する、又は重合開始可 能な官能基を有する重合開始層が形成された基板を作製する工程と、（al— 2)該重 合開始層に、めっき触媒又はその前駆体と相互作用を形成する官能基、及び重合 性基を有するポリマーを直接化学結合させる工程を含むことを特徴とする請求項 1又 は請求項 2に記載の表面金属膜材料の作製方法。 [4] The step (al) includes (al-1) a step of producing a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a base material. And (al-2) comprising a step of directly chemically bonding a polymer having a polymerizable group and a functional group that interacts with the plating catalyst or a precursor thereof to the polymerization initiating layer. A method for producing a surface metal film material according to claim 1. [5] 前記めつき触媒又はその前駆体と相互作用を形成する官能基、及び重合性基を 有するポリマーが、下記式（1)で表されるユニット、及び、下記式（2)で表されるュニ ットを含む共重合体であることを特徴とする請求項 3又は請求項 4に記載の表面金属 膜材料の作製方法： [5] A functional group capable of interacting with the plating catalyst or a precursor thereof, and a polymerizable group. The polymer according to claim 3 or 4, wherein the polymer is a copolymer including a unit represented by the following formula (1) and a unit represented by the following formula (2). Method for producing the described surface metal film material: [化 37]  [Chemical 37]
Figure imgf000120_0001
式 《1 ) 式 ( 2 ) 式（1)及び式（2)中、！^〜 は、各々独立に、水素原子、又は置換もしくは無置換 のアルキル基を表し; X、 Y及び Zは、各々独立に、単結合、又は置換もしくは無置換 の二価の有機基、エステル基、アミド基、又はエーテル基を表し； L1及び L2は、各々 独立に、置換もしくは無置換の二価の有機基を表す。
Figure imgf000120_0001
Formula << 1) Formula (2) In Formula (1) and Formula (2),! ^ ~ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group; X, Y and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group or ester group. , an amide group or an ether group; L 1 and L 2 each independently represents a substituted or unsubstituted divalent organic group. [6] 前記めつき触媒又はその前駆体と相互作用を形成する官能基、及び重合性基を 有するポリマーの重量平均分子量が 20000以上であることを特徴とする請求項 3〜 請求項 5のいずれか 1項に記載の表面金属膜材料の作製方法。  [6] The weight average molecular weight of the polymer having a functional group that interacts with the catalyst or a precursor thereof and a polymerizable group is 20000 or more, and any one of claims 3 to 5 The method for producing a surface metal film material according to claim 1. [7] 前記官能基がシァノ基であることを特徴とする請求項 1に記載の表面金属膜材料 の作製方法。  [7] The method for producing a surface metal film material according to [1], wherein the functional group is a cyano group. [8] 前記（a3)工程が、無電解めつき工程を含むことを特徴とする請求項 1〜請求項 7の いずれか 1項に記載の表面金属膜材料の作製方法。  [8] The method for producing a surface metal film material according to any one of [1] to [7], wherein the step (a3) includes an electroless plating step. [9] 前記無電解めつき工程の後に、更に電気めつき工程を含むことを特徴とする請求 項 8に記載の表面金属膜材料の作製方法。 9. The method for producing a surface metal film material according to claim 8, further comprising an electric plating process after the electroless plating process. [10] 前記めつき触媒力 Sパラジウムであることを特徴とする請求項 1〜請求項 9のいずれ 力、 1項に記載の表面金属膜材料の作製方法。 [10] The catalyst power according to any one of claims 1 to 9, wherein the catalytic power S is palladium. 2. A method for producing a surface metal film material according to item 1. [11] 請求項 1〜請求項 10のいずれか 1項に記載の表面金属膜材料の作製方法により 得られた表面金属膜材料。 [11] A surface metal film material obtained by the method for producing a surface metal film material according to any one of claims 1 to 10. [12] シァノ基及び重合性基を有するポリマーと、該ポリマーを溶解しうる溶剤と、を含有 し、請求項 1〜請求項 10のいずれか 1項に記載の表面金属膜材料の作製方法に用 いられることを特徴とするポリマー層形成用組成物。  [12] The method for producing a surface metal film material according to any one of claims 1 to 10, comprising a polymer having a cyano group and a polymerizable group, and a solvent capable of dissolving the polymer. A polymer layer forming composition characterized by being used. [13] - 0- (CH ) - 0 - (nは 1〜5の整数)で表される構造、及び重合性基を有する  [13]-0- (CH)-0-(n is an integer of 1 to 5) and having a polymerizable group 2 n  2 n ポリマーと、該ポリマーを溶解しうる溶剤と、を含有し、請求項 1〜請求項 4、及び請求 項 8〜； 10のいずれか 1項に記載の表面金属膜材料の作製方法に用いられることを特 徴とするポリマー層形成用組成物。  A polymer and a solvent capable of dissolving the polymer, and used in the method for producing a surface metal film material according to any one of claims 1 to 4 and claims 8 to 10. A composition for forming a polymer layer. [14] (a4)請求項 1〜請求項 10のいずれか 1項に表面金属膜材料の作製方法により得 られた表面金属膜材料のめっき膜をパターン状にエッチングする工程を有することを 特徴とする請求項 1に記載の金属パターン材料の作製方法。 [14] (a4) The method according to any one of claims 1 to 10, further comprising a step of etching a plating film of the surface metal film material obtained by the method for producing the surface metal film material into a pattern. The method for producing a metal pattern material according to claim 1. [15] 請求項 14に記載の金属パターン材料の作製方法により得られた金属パターン材 料。 [15] A metal pattern material obtained by the method for producing a metal pattern material according to claim 14. [16] 前記（al)工程が、（al")前記基板である樹脂フィルムの両面に対して、めっき触媒 又はその前駆体と相互作用を形成する官能基を有し、且つ、該基板と直接化学結合 したポリマーからなる前記ポリマー層を形成する工程であることを特徴とする請求項 1 に記載の表面金属膜材料の作製方法。  [16] The step (al) includes (al ") a functional group that interacts with the plating catalyst or a precursor thereof on both sides of the resin film as the substrate, and directly with the substrate. 2. The method for producing a surface metal film material according to claim 1, which is a step of forming the polymer layer made of a chemically bonded polymer. [17] 前記（al")工程、前記（a2)工程、及び前記（a3)工程が、各工程毎に、前記樹脂 フィルムの両面に対して同時に行われることを特徴とする請求項 16に記載の表面金 属膜材料の作製方法。  [17] The method according to claim 16, wherein the step (al "), the step (a2), and the step (a3) are simultaneously performed on both surfaces of the resin film for each step. For producing a surface metal film material. [18] 下記式（1)で表されるユニット、及び、下記式（2)で表されるユニットを含むことを特 徴とするポリマー：  [18] A polymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2): [化 38]
Figure imgf000122_0001
[Chemical 38]
Figure imgf000122_0001
 式 ( 1 ) 式 （2 ) 式（1)及び式（2)中、！^〜 は、各々独立に、水素原子、又は置換もしくは無置換 のアルキル基を表し; X、 Y及び Zは、各々独立に、単結合、置換もしくは無置換の二 価の有機基、エステル基、アミド基、又はエーテル基を表し； L1及び L2は、各々独立 に、置換もしくは無置換の二価の有機基を表す。 Formula (1) Formula (2) In Formula (1) and Formula (2),! ^ ~ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group; X, Y and Z each independently represent a single bond, a substituted or unsubstituted divalent organic group, an ester group, Represents an amide group or an ether group; L 1 and L 2 each independently represents a substituted or unsubstituted divalent organic group; [19] 前記式（1)で表されるユニットが、下記式（3)で表されるユニットであることを特徴と する請求項 18に記載のポリマー：  [19] The polymer according to [18], wherein the unit represented by the formula (1) is a unit represented by the following formula (3): [化 39]  [Chemical 39]
Figure imgf000122_0002
Figure imgf000122_0002
 式 ( 3 )  Formula (3) 式（3)中、 R1及び R2は、各々独立に、水素原子、又は置換もしくは無置換のアルキ ル基を表し; Zは、単結合、置換もしくは無置換の二価の有機基、エステル基、アミド 基、又はエーテル基を表し; Wは、酸素原子、又は NRを表し、ここで Rは、水素原子 、又はアルキル基を表し;かつ、 L1は、置換もしくは無置換の二価の有機基を表す。 In formula (3), R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group; Z represents a single bond, a substituted or unsubstituted divalent organic group, an ester Group, amide W represents an oxygen atom or NR, wherein R represents a hydrogen atom or an alkyl group; and L 1 represents a substituted or unsubstituted divalent organic group. To express. [20] 前記式（3)で表されるユニットが、下記式 (4)で表されるユニットであることを特徴と する請求項 19に記載のポリマー：  [20] The polymer according to claim 19, wherein the unit represented by the formula (3) is a unit represented by the following formula (4): [化 40]  [Chemical 40]
Figure imgf000123_0001
Figure imgf000123_0001
 式 （4》 式 (4)中、 R1及び R2は、各々独立に、水素原子、又は置換もしくは無置換のアルキ ル基を表し; V及び Wは、各々独立に、酸素原子、又は NRを表し、ここで Rは、水素 原子、又はアルキル基を表し;かつ、 L1は、置換もしくは無置換の二価の有機基を表 す。 Formula (4) In Formula (4), R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group; V and W each independently represent an oxygen atom or NR Where R represents a hydrogen atom or an alkyl group; and L 1 represents a substituted or unsubstituted divalent organic group. [21] 前記式 (4)における Wが酸素原子であることを特徴とする請求項 20に記載のポリマ  21. The polymer according to claim 20, wherein W in the formula (4) is an oxygen atom. 〇  Yes [22] 前記式（1)、式（3)、又は式 (4)における L1がウレタン結合又はウレァ結合を有する 二価の有機基であることを特徴とする請求項 18〜請求項 21のいずれか 1項に記載 のポリマー。 [22] In the formula (1), the formula (3), or the formula (4), L 1 is a divalent organic group having a urethane bond or a urea bond. The polymer according to any one of the above. [23] 前記式式（1)、式（3)、又は（4)における L1が総炭素数 1〜9である二価の有機基 であることを特徴とする請求項 18〜請求項 22のいずれ力、 1項に記載のポリマー。 [23] Formula Formula (1), equation (3), or claim 18 claim 22, L 1 in (4) is characterized in that it is a divalent organic group having 1 to 9 carbon atoms in total Any one of the forces, the polymer according to 1. [24] 前記式（2)で表されるユニットが、下記式（5)で表されるユニットであることを特徴と する請求項 18〜請求項 23のいずれ力、 1項に記載のポリマー： [化 41] [24] The polymer according to any one of claims 18 to 23, wherein the unit represented by the formula (2) is a unit represented by the following formula (5): [Chemical 41]
Figure imgf000124_0001
式 ( 5 ) 式（5)中、 R5は、水素原子、又は置換もしくは無置換のアルキル基を表し; Uは、酸 素原子、又は NR' を表し、ここで R'は、水素原子、又はアルキル基を表し；かつ、 L2 は、置換もしくは無置換の二価の有機基を表す。
Figure imgf000124_0001
In the formula (5) (5), R 5 represents a hydrogen atom, or a substituted or unsubstituted alkyl group; U is 'represents, wherein R' acid atom, or NR a hydrogen atom, or an alkyl group; and, L 2 represents a substituted or unsubstituted divalent organic group. [25] 前記式（5)における L2中のシァノ基との連結部位力 直鎖、分岐、又は環状のアル キレン基を有する二価の有機基であることを特徴とする請求項 24に記載のポリマー。 [25] linking site power linear with Shiano group in L 2 in Formula (5), branched, or claim 24, which is a divalent organic group having a cyclic Al Killen group Polymer. [26] 前記二価の有機基の総炭素数が 1〜； 10であることを特徴とする請求項 25に記載の ポリマー。 26. The polymer according to claim 25, wherein the divalent organic group has a total carbon number of 1 to 10; [27] 前記式（5)における L2中のシァノ基との連結部位力 芳香族基を有する二価の有 機基であることを特徴とする請求項 24に記載のポリマー。 [27] The polymer according to claim 24 which is a divalent organic group having a linking site force aromatic group with Shiano group in L 2 in Formula (5). [28] 前記二価の有機基の総炭素数が 6〜； 15であることを特徴とする請求項 27に記載の ポリマー。 28. The polymer according to claim 27, wherein the divalent organic group has a total carbon number of 6 to 15; [29] 前記式（5)における R5が水素原子であることを特徴とする請求項 24〜請求項 28の いずれか 1項に記載のポリマー。 [29] The polymer according to any one of claims 24 to claim 28, R 5 in Formula (5) is characterized in that it is a hydrogen atom. [30] 前記式（1)、式（3)、又は式 (4)における L1がウレタン結合を有する二価の有機基 であることを特徴とする請求項 18〜請求項 29のいずれ力、 1項に記載のポリマー。 [30] The power according to any one of claims 18 to 29, wherein L 1 in the formula (1), the formula (3), or the formula (4) is a divalent organic group having a urethane bond. The polymer according to item 1. [31] 重量平均分子量が 2万以上であることを特徴とする請求項 18〜請求項 30のいず れか 1項に記載のポリマー。 [31] The polymer according to any one of claims 18 to 30, wherein the polymer has a weight average molecular weight of 20,000 or more. [32] 請求項 30に記載のポリマーの合成方法であって、 少なくとも溶媒中で、側鎖にヒドロキシル基を有するポリマー、及び、イソシァネート 基と重合性基とを有する化合物を用い、該ヒドロキシル基に該イソシァネート基を付 加させることにより前記 L1中のウレタン結合を形成する工程を含むことを特徴とするポ リマーの合成方法。 [32] The method for synthesizing a polymer according to claim 30, In at least a solvent, a polymer having a hydroxyl group in the side chain, and a compound having a polymerizable group and Isoshianeto group, a urethane bond in the L 1 by pressing with the Isoshianeto group to the hydroxyl group A method for synthesizing a polymer, comprising the step of forming. [33] 前記側鎖にヒドロキシル基を有するポリマー力 S、下記ひ）〜（4)の工程を順次経るこ とで得られたヒドロキシル基含有 (メタ）アタリレートを用いて合成されたものであること を特徴とする請求項 32に記載のポリマーの合成方法：  [33] Polymer power S having a hydroxyl group in the side chain, which is synthesized using hydroxyl group-containing (meth) acrylate obtained through the steps of (4) to (4) below. A method for synthesizing a polymer according to claim 32, characterized in that: (1)ヒドロキシノレ基含有 (メタ）アタリレートと、該ヒドロキシノレ基含有 (メタ）アタリレートを 合成する際に副生する 2官能アタリレートと、を含む混合物を、水に溶解する工程 (1) A step of dissolving, in water, a mixture containing a hydroxyl group-containing (meth) acrylate and a bifunctional acrylate which is by-produced when synthesizing the hydroxyl group-containing (meth) acrylate. (2)得られた水溶液に、水と分離する第 1の有機溶剤を加えた後、該第 1の有機溶剤 と前記 2官能アタリレートとを含む層を水層から分離する工程 (2) A step of adding a first organic solvent that separates from water to the obtained aqueous solution, and then separating a layer containing the first organic solvent and the bifunctional acrylate from the aqueous layer. (3)前記水層に、前記ヒドロキシル基含有 (メタ）アタリレートよりも水溶解性の高!/、化 合物を溶解する工程  (3) A step of dissolving a compound having a higher water solubility than the hydroxyl group-containing (meth) acrylate in the aqueous layer. (4)前記水層に第 2の有機溶剤を加えて、前記ヒドロキシル基含有 (メタ）アタリレート を抽出した後、濃縮する工程。  (4) A step of adding a second organic solvent to the aqueous layer to extract the hydroxyl group-containing (meth) acrylate, and then concentrating. [34] 前記（1)〜（4)の工程を順次経ることで得られたヒドロキシル基含有 (メタ）アタリレ ートを含む単離物が、その全質量中に前記 2官能アタリレートを 0質量％以上 0. 10 質量％以下の範囲で含むことを特徴とする請求項 33に記載のポリマーの合成方法。  [34] An isolate containing a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the steps (1) to (4) described above has 0 mass of the bifunctional acrylate in the total mass. 34. The method for synthesizing a polymer according to claim 33, wherein the polymer is contained in the range of not less than 0.1% and not more than 0.10% by mass. [35] 前記溶媒の SP値 (沖津法により算出）が 20〜23MPa1/2であることを特徴とする請 求項 32〜請求項 34のいずれか 1項に記載のポリマーの合成方法。 [35] The method for synthesizing a polymer according to any one of claims 32 to 34, wherein the solvent has an SP value (calculated by the Okitsu method) of 20 to 23 MPa 1/2 . [36] 前記溶媒がエステル系溶媒であることを特徴とする請求項 35に記載のポリマーの 合成方法。  [36] The method for synthesizing a polymer according to [35], wherein the solvent is an ester solvent. [37] 前記溶媒がジアセテート系溶媒であることを特徴とする請求項 36に記載のポリマー の合成方法。  37. The polymer synthesis method according to claim 36, wherein the solvent is a diacetate solvent. [38] 請求項 18〜請求項 31のいずれ力、 1項に記載のポリマーと、ケトン系溶剤又は二トリ ル系溶剤と、を含有する組成物。  [38] A composition comprising the polymer according to any one of claims 18 to 31, and a ketone solvent or a nitrile solvent. [39] 請求項 18〜請求項 31のいずれか 1項に記載のポリマーの濃度力 2質量％〜50 質量％であることを特徴とする請求項 38に記載の組成物。 [40] 請求項 38又は請求項 39に記載の組成物を、樹脂基材上に塗布してなる積層体。 39. The composition according to claim 38, wherein the concentration power of the polymer according to any one of claims 18 to 31 is 2% by mass to 50% by mass. [40] A laminate obtained by applying the composition according to claim 38 or claim 39 onto a resin substrate.
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